Aqueous synthetic resin dispersion

ABSTRACT

A aqueous dispersion comprising particles of at least one resin selected from the group consisting of a polyaddition type resin, a polycondensation type resin, an addition condensation type resin, a ring-opening-polymerization type resin and an addition polymerization type resin; wherein the particle has at least two peaks in a particle diameter distribution curve; at least one of the peaks comprises at least one resin selected from the group consisting of a polyaddition type resin, a polycondensation type resin, an addition condensation type resin and a ring-opening-polymerization type resin. The aqueous dispersion exhibits a low viscosity even at a high concentration exceeding 65%, and has better stability with day. In addition, a paint, an adhesive, a pressure-sensitive adhesive and a fiber and textile processing agent using the dispersion of the present invention is excellent in storage stability even at a high concentration.

TECHNICAL FIELD

The present invention relates to an aqueous resin dispersion, inparticular, an aqueous synthetic resin dispersion useful in paints,adhesives, pressure-sensitive adhesives and fiber and textile processingand treating agents.

BACKGROUND TECHNIQUE

Previously, as a process for preparing an aqueous high solid resindispersion, a method of polymerizing a vinyl-based monomer in thepresence of a pre-formed seed latex (U.S. Pat. Nos. 3,424,706 and4,130,523) has been known.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an aqueous syntheticresin dispersion having a low viscosity even at a high concentration.

Another object of the present invention is to provide an aqueoussynthetic resin dispersion excellent in storage stability.

A further object of the present invention is to provide a quick-dryinghighly concentrated aqueous synthetic resin dispersion.

Still another object of the present invention is to provide an aqueoussynthetic resin dispersion excellent in film forming property at drying.

A further other object of the present invention is to provide an aqueouspaint which is excellent in coating suitability and can be coated at alarge thickness.

The above and following other objects of the present invention can beattained by an aqueous dispersion comprising resin particles having atleast two peaks in a particle diameter distribution curve and satisfyingone or both of the following (i) and (ii):

(i) in a particle diameter distribution curve, a peak (P1) having alarger particle diameter and a peak (P2) having a smaller particlediameter among a highest peak and a second highest peak give a ratio ofa peaktop particle diameter (P1)/a peaktop particle diameter of (P2), ina range of 2/1 to 100/1, and a ratio of a height of (P1)/a height of(P2) in a range of 1/1 to 10/1, both of (P1) and (P2) have a peakvariation coefficient of 0.1 to 150%, a skewness of −10 to 10 andkurtosis of 0 to 10; and

(ii) in a concentration range of an aqueous dispersion of 20 to 70%, theaqueous dispersion satisfies the following relationship equation (1)having a coefficient A of −2 to 0 and a constant item B of 1 to 5:1/log(η/η₀)=Aφ+B  (1)wherein η₀ and η represent Brookfield viscosities (mPa·s, 25° C.) ofwater and an aqueous dispersion having a resin concentration of φ% byweight (hereinbefore and hereinafter, % represents % by weight unlessotherwise indicated).

The aqueous dispersion comprises particles of at least one resinselected from the group consisting of a polyaddition type resin, apolycondensation type resin, an addition condensation type resin, aring-opening-polymerization type resin and an addition polymerizationtype resin.

At least one peak among peaks in a particle diameter distribution curvecomprises at least one resin selected from the group consisting of apolyaddition type resin, a polycondensation type resin, an additioncondensation type resin and a ring-opening-polymerization type resin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 and FIG. 2 are a graph showing relationship between a particlediameter and a scattering intensity in particle diameter distribution. Apoint v in the figures shows a lowest valley (minimal point) presentbetween (P1) and (P2) in a particle diameter distribution curve.

DETAILED DISCLOSURE OF THE INVENTION

Particle Diameter Distribution Curve

In one aspect of the present invention, an aqueous resin dispersionsatisfying the aforementioned requirement (i) [hereinafter, referred toas aqueous dispersion (I)] has a specified particle diameterdistribution curve described below.

A particle diameter distribution curve is a histogram format particlediameter distribution curve which is produced by measuring weightdistribution of a particle diameter at a normal temperature by a photoncorrelation or an ultrasonic measuring method, and in which a particlediameter is an abscissa and a scattering intensity is a ordinate. As anapparatus used for measurement, “ELS-2000” manufactured by OtsukaElectronics Co., Ltd. can be used in a photon correlation method, and“DT-1200” manufactured by Nihon Rufuto Co., Ltd. can be used in anultrasonic measuring method. A photon correlation method is a preferablemeasuring method in that resolution is better in a submicron region.

An aqueous resin dispersion (I) has preferably 2 to 8, furtherpreferably 2 to 4, particularly preferably 2 peaks in a particlediameter distribution curve in that an aqueous dispersion having a highconcentration and a low viscosity is given.

In a particle diameter distribution curve, a peak (P1) having a largerparticle diameter and a peak (P2) having a smaller particle diameteramong a highest peak and a second highest peak have a ratio of a peaktopparticle diameter of (P1)/a peaktop particle diameter of (P2) of atleast 2/1 (preferably at least 2.2/1, particularly preferably at least2.5/1), and a ratio of a height of (P1)/a height of (P2) of at least 1/1(preferably at least 1.5/1, particularly preferably at least 1.8/1),whereby, better storage stability is imparted; have a ratio of a peaktopparticle diameter of (P1)/a peaktop particle diameter of (P2) of at most100/1 (preferably at most 20/1, particularly preferably at most 15/1),and a ratio of a height of (P1)/a height of (P2) at most 10/1(particularly at most 5/1), whereby, it becomes possible to retain a lowviscosity even at a high concentration.

(P1) and (P2) have a variation coefficient of usually 0.1 to 150%(preferably 1 to 100%, particularly preferably 15 to 70%), a skewness of−10 to 10 (preferably −5 to 5, particularly preferably 0 to 2), and akurtosis of 0 to 10 (preferably 0.5 to 10, particularly preferably 1 to5), whereby an aqueous dispersion having a low viscosity is given. Avariation coefficient, a skewness and a kurtosis of a peak arecalculated by the following equations (2), (3), and (4) respectively.

$\begin{matrix}{{{Variation}\mspace{14mu}{coefficient}} = {\left( {s/x_{i}} \right) \times 100}} & (2) \\{{Skewness} = {\sum\limits_{i = 1}^{n}{{\left( {x_{i} - x} \right)^{3}/n} \cdot s^{3}}}} & (3) \\{{Kurtosis} = {\sum\limits_{i = 1}^{n}{{\left( {x_{i} - x} \right)^{4}/n} \cdot s^{4}}}} & (4)\end{matrix}$

In the equations, X represents a scattering intensity in each particlediameter, X_(i) represents an average of a scattering intensity at eachparticle diameter, n represents a degree of freedom, and s representsstandard deviation of a peak which can be calculated by the followingequation (5).

$\begin{matrix}{s = \sqrt{\frac{1}{n - 1} \times {\sum\limits_{i = 1}^{n}\left( {x_{i} - x} \right)^{2}}}} & (5)\end{matrix}$Relationship Between Concentration and Viscosity

In other aspect of the present invention, an aqueous resin dispersionsatisfying the aforementioned requirement (ii) [hereinafter, referred toas aqueous dispersion (II)] has relationship between a concentration φand a viscosity μ indicated by the aforementioned equation (1), in arange of a concentration of an aqueous dispersion of 20 to 70%. Theequation (1) was derived from the Maron's equation applying to a highlyconcentrated dispersion system [“Chemistry of Polymer Latex” (authoredby Soichi Muroi, published in 1965) p. 138].

A coefficient A and a constant item B in the equation (1) are calculatedby the following method.

1) An aqueous dispersion is diluted or concentrated to prepare anaqueous dispersion having a resin concentration φ adjusted to 35, 45, 55and 65%.

2) Brookfield viscosities η of aqueous dispersions having respectiveconcentrations are measured.

3) A viscosity η₀ of water is measured.

4) A linear expression representing relationship between φ and 1/log(η/η₀) is obtained by a method of least squares, and a coefficient A anda constant item B are calculated.

The equation (1) is usually regressed by a linear expression and, when acontribution rate of φ to 1/log (η/η₀) is less than 0.6, approximationby quadratic or higher polynomial, or approximation by power can beperformed. In that case, a rate of change in 1/log (η/η₀) relative to φis taken as a coefficient A.

A concentration φ is such that 1 to 1.5 g of a sample is preciselyweighed in a glass laboratory dish having a diameter of 9 cm, heated andevaporated to dryness in a circulating drier at 130° C. for 45 minutes,a weight of a remainder is precisely weighed, and a weight of a reminderrelative to a sample weight is expressed by percentage. Adjustment ofrespective concentrations is performed by diluting with water, orconcentrating by distilling water off and, in the latter (e.g. in thecase of an aqueous dispersion having a concentration of lower than 65%),adjustment is performed by heating (at 40 to 60° C.) an aqueousdispersion under reduced pressure.

A viscosity can be measured using a rotatory viscometer manufactured byTOKIMEC (K.K.). A viscosity is measured using a No.1 rotor in the caseof 20 to 150 mPa·s, a No.2 rotor in the case of larger than 150 mPa·sand not larger than 750 mPa·s, a No.3 rotor in the case of larger than750 mPa·s and not larger than 3,000 mPa·s, and a No.4 rotor in the caseof larger than 3,000 mPa·s and not larger than 20,000 mPa·s, at arotation number of 60 rpm in any cases.

An aqueous dispersion (II) has a coefficient A of usually at least −2(preferably at least −1, particularly preferably at least −0.5) and aconstant item B of at least 1 (preferably at least 1.1, particularlypreferably at least 1.15) from a viewpoint that a low viscosity isimparted; has a coefficient A of at most 0 (preferably at most −0.001,particularly preferably at most −0.015) and a constant item B of at most5 (preferably at most 4.5, particularly preferably at most 3) from aviewpoint of the stability with day (difficulty of particle settling).

Among aqueous dispersions (I) and (II), a preferable dispersion is anaqueous dispersion (I) satisfying the aforementioned requirement (i), inparticular, satisfying the aforementioned requirements (i) and (ii),from a viewpoint that an aqueous dispersion having a lower viscosity iseasily obtained.

The aqueous dispersion [(I) and (II)] of the present invention has aconcentration of usually 30 to 80%, preferably 50 to 75%, morepreferably 60 to 70%.

A viscosity (25° C.) of the aqueous dispersion of the present inventionis different depending on a concentration. At a concentration of 65%, aviscosity is usually 10 to 20,000 mPa·s, preferably 20 to 10,000 mPa·s,particularly preferably 30 to 5,000 mPa·s.

Synthetic Resin Constituting Aqueous Dispersion

The aqueous dispersion of the present invention comprises particles ofat least one resin selected from the group consisting of a polyadditiontype resin, a polycondensation type resin, an addition condensation typeresin, a ring-opening-polymerization type resin and an additionpolymerization type resin.

In the aqueous dispersion of the present invention, at least one peakamong peaks in a particle diameter distribution curve comprises at leastone resin selected from the group consisting of a polyaddition typeresin, a polycondensation type resin, an addition condensation typeresin and a ring-opening-polymerization type resin, and a resinconstituting other peak may be an addition polymerization type resin.

Examples of a polyaddition type resin includes a polyurethane resin;examples of a polycondensation type resin includes a polyester resin, asilicone resin, a polyamide resin and a polycarbonate resin; examples ofan addition polymerization type resin includes a vinyl-based resin (e.g.acrylic resin, styrene/alkadiene-based resin and vinyl acetate-basedresin); examples of an addition condensation type resin includes aphenol resin and an amino resin (e.g. urea resin and melamine resin);examples of a ring-opening-polymerization type resin includes an epoxyresin.

Among these resins, a preferable resin is at least one resin selectedfrom the group consisting of a polyaddition type resin, apolycondensation type resin and a polyaddtion type resin, and/or jointuse of a polycondensation type resin and an addition polymerization typeresin, in particular, joint use of one or more selected from the groupconsisting of a polyurethane resin (U), a polyester resin (E), and jointuse of (U) and/or (E) and an acrylic resin (M) and/or astyrene/alkadiene-based resin (D).

The aqueous dispersion of the present invention has at least two peaksin a particle diameter distribution curve, and kinds of resinsconstituting those peaks may be the same or different. A preferablecombination in the case of different is (U)/(E) and (U)/(M).

(U) is obtained by reacting active hydrogen atom-containing componentscomprising organic polyisocyanate (a1) and polyol (a2).

As (a1), organic polyisocyanates which have been previously used inpreparation of polyurethane can be used. Such the polyisocyanateincludes aromatic polyisocyanate of a carbon number (hereinafter,abbreviated C) (except for carbons in NCO group, same hereinafter) of 6to 20 having 2 to 3 or more isocyanate groups, C2 to C18 aliphaticpolyisocyanate, C4 to C15 alicyclic polyisocyanate, C8 to C15 aromaticaliphatic polyisocyanate, and modification of these polyisocyanates, aswell as joint use of two or more of them.

Examples of aromatic polyisocyanate include 1,3- and/or 1,4-phenylenediisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TDI), crude TDI,4,4′- and/or 2,4′-diphenylmethane diisocyanate (MDI), phosgenized crudeMDI [crude diaminophenylmethane [a condensation product of formaldehydeand aromatic amine (aniline) or a mixture thereof; a mixture ofdiaminodiphenylmethane and a small amount (e.g. 5 to 20% by weight) oftri- or more-functional polyamine]: polyaryl polyisocyanate (PAPI)],4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl,3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthalenediisocyanate, 4,4′,4″-triphenylmethane triisocyanate, m- andp-isocyanatophenylsulfonyl isocyanate; aliphatic polyisocyanate such asethylene diisocyanate, tetramethylene diisocyanate, hexamethylenediisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecanetriisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysinediisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl) carbonate,2-isocyanatoethyl-2,6-diisocyanatohexanoate; alicyclic polyisocyanatesuch as isophorone diisocyanate (IPDI),dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylenediisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI),bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or2,6-norbornane diisocyanate; aromatic aliphatic polyisocyanate such asm- and/or p-xylene diisocyanate (XDI), α,α,α′,α′-tetramethylxylylenediisocyanate (TMXDI); modified polyisocyanate such as modifiedaforementioned polyisocyanate (urethane group, carbodiimide group,allophanate group, urea group, biuret group, uretodione group,uretoimine group, isocyanurate group and/or oxazolidone group-containingmodified polyisocyanate; free isocyanate group content is usually 8 to33%, preferably 10 to 30%, particularly preferably 12 to 29%), andmodified polyisocyanate such as modified MDI (urethane-modified MDI,carbodiimido-modified MDI, trihydrocarbylphosphate-modified MDI etc.),urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI,and isocyanurate-modified IPDI. Examples of polyol used in preparationof urethane-modified polyisocyanate [free isocyanate-containingprepolymer obtained by reacting excessive polyisocyanate (TDI, MDI) withpolyol] include low-molecular polyol described later. Examples of jointuse of two or more include joint use of modified MDI andurethane-modified TDI (isocyanate-containing prepolymer). Among them,preferable aromatic polyisocyanate includes aromatic polyisocyanateshaving the number of functional groups of 2 to 3, particularly TDI, MDI,HDI, IPDI, hydrogenated MDI, XDI and TMXDI.

Examples of (a2) include a high-molecular polyol having a hydoxyl groupequivalent (Mn per hydroxyl group) of 150 or more (a21) and alow-molecular polyol (a22), and joint use of two or more of them[hereinbefore and hereinafter, Mn represents a number average molecularweight measured using gel permeation chromatography (GPC)].

Examples of (a21) include polyesterpolyol (a211), polyetherpolyol(a212), polyolefinpolyol (a213) and polymer polyol (a214). Examples of(a211) include condensed type polyester (a2111), polylactonepolyol(a2112), polycarbonatepolyol (a2113) and castor oil-based polyol(a2114). Examples of (a212) include an alkylene oxide (hereinafter,abbreviated as AO) adduct of active hydrogen atom-containing compound(a2121), and a coupled adduct (a2122).

Examples of (a22) include polyhydric alcohol (a221), dihydric tooctahydric or more-hydric, having a hydroxyl group equivalent of notsmaller than 30 and less than 150, and an AO low mol adduct (a222) of anactive hydrogen atom-containing compound.

Examples of (a221) include dihydric alcohol such as C2 to C12 or higheraliphatic, alicyclic and aromatic dihydric alcohol [(di)alkylene glycol(represents alkylene glycol and dialkylene glycol)]. Hereinafter, (sameexpression is used), such as (di)ethylene glycol, (di)propylene glycol,1,2-, 1,3-, 2,3- and 1,4-butanediol, neopentyl glycol,3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol,1,9-nonanediol and 1,12-dodecanediol; low-molecular diol having a cyclicgroup, for example, those described in JP-B No.45-1474:bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)benzene etc.); trihydricto octahydric or more-hydric polyhydric alcohol such as alkanepolyol(triol such as trimethylolpropane, glycerin and hexanetriol; tetra- ormore-hydric highly functional polyol such as pentaerythritol, sorbitol,xylitol and mannitol), intermolecular or intramolecular dehydrate ofthem (diglycerin, dipentaerythritol, sorbitan, etc.), sugars (glucose,fructose, sucrose, etc.) and derivative thereof (for example, glycosidesuch as α-methylglycoside); as well as hydrophilic group-containingpolyol described later.

Examples of AO used in preparation of (a2121) and (a222) include C2 toC12 or higher AO, such as ethylene oxide (EO), propylene oxide (PO),1,2-, 1,3- and 1,3-butylene oxide, tetrahydrofuran (THF), α-olefinoxide, styrene oxide, epihalohydrin (epichlorohydrin etc.), and jointuse of these two or more (random and/or block).

Examples of an active hydrogen atom-containing compound used inpreparation of (a212) and (a222) include compounds having 2 to 8 or moreactive hydrogen atoms (compounds one or more of hydroxyl group, aminogroup, mercapto group, carboxyl group, etc.); such as polyhydricalcohol, polyhydric phenols, amines, polycarboxylic acid, phosphoricacids, polythiol and a mixture of two or more of them. Examples ofpolyhydric alcohol include the aforementioned polyhydric alcoholsexamples of polyhydric phenols include monocyclic polyhydric phenols(pyrogallol, catechol, hydroquinone, etc.), and bisphenols (bisphenol A,bisphenol F, bisphenol S, etc.).

Examples of amines include monoamines and polyamines. Examples ofmonoamines include ammonia; primary monoamine such as C1 to C20monohydrocarbyl (alkyl, cycloalkyl, aryl, aralkyl) amine (butylamine,cyclohexylamine, aniline, benzylamine); and alkanolamines (C2 to C4alkanolamines having hydroxyalkyl group; monoethanolamine,diethanolamine, triethanolamine, triisopropanolamine).

Examples of polyamines include C2 to C18 aliphatic polyamines [e.g.alkylene diamine (ethylene diamine, trimethylenediamine,hexamethylenediamine, etc.), and polyalkylenepolyamine(diethylenetriamine)], C4 to C15 alicyclic polyamines(dicyclohexylmethanediamine, isophoronediamine, etc.), C8 to C15aromatic aliphatic polyamines (xylylenediamine, etc.), C6 to C20aromatic polyamines (phenylenediamine, tolylenediamine,diethyltolylenediamine, diphenylmethane diamine, diphenyletherdiamine,polyphenylmethanepolyamine, etc.), and heterocyclic polyamines(piperazine, N-aminoethylpiperazine and those described in JP-BNo.55-21044).

Examples of polycarboxylic acid include divalent to octavalent ormore-valent C4 to C40 or more aliphatic, alicyclic and aromaticcarboxylic acids; examples include dicarboxylic acids such as aliphaticdicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacicacid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids(dimer acid, etc.) and aromatic dicarboxylic acids (terephthalic acid,isophthalic acid, phthalic acid, etc.), as well as tri- or more-valentpolycarboxylic acids (trimellitic acid, pyromellitic acid, etc.).

Examples of phosphoric acids include phosphoric acid, phosphorous acid,phosphonic acid; examples of polythiol include polythiols (in which atleast a part of OHs are substituted with SHs) corresponding to theaforementioned polyhydric alcohols, and polythiols obtained by reactinga glycidyl group-containing compound and hydrogen sulfide.

Addition of AO to an active hydrogen atom-containing compound can beperformed by the conventional method, and can be performed under normalpressure or under pressure without a catalyst or in the presence of acatalyst (e.g. alkali catalyst, amine-based catalyst, acidiccatalyst)(particularly, at a later stage of AO addition) at a one stageor a multiple stage. For example, there is a method of charging anactive hydrogen atom-containing compound and a catalyst in a pressurereactor, and pressing AO therein. Examples of a catalyst include alkalicatalysts such as hydroxides of alkali metals (lithium, sodium,potassium, cesium, etc.); acids [perhalogenoic acid (perchloric acid,perbromic acid, periodic acid), sulfuric acid, phosphoric acid, nitricacid, preferably perchloric acid] and salts thereof [preferably salts ofdivalent or trivalent metals (Mg, Ca, Sr, Ba, Zn, Co, Ni, Cu, Al)]. Areaction temperature is usually 50 to 150° C. and a reaction time isusually 2 to 20 hours.

Joint use of two or more kinds of AOs may be block addition (chip type,balance type, active secondary type, etc.), random addition or mixedsystem of both of them [chipping after random addition: 0 to 50% byweight (preferably 5 to 40% by weight) of an ethylene oxide chainarbitrarily dispersed in a molecule is possessed, and 0 to 30% by weight(preferably 5 to 25% by weight) of an EO chain is chipped at a molecularend]. Among AOs, preferable are EO alone, PO alone, THF alone, joint useof PO and EO, and joint use of P0 and/or EO and THF (in the case ofjoint use, random, block and mixed system of both of them).

The addition mole number of AO is usually 1 to 140, preferably 1 to 110,particularly preferably 1 to 90 per active hydrogen atom. When theaddition mole number exceeds 140, the resulting polyurethane resinbecomes soft, and a strength thereof is reduced.

After completion of the AO addition reaction, a catalyst can beneutralized, and the catalyst can be removed and purified by treatingwith an adsorbent, as necessary.

Examples of (a2121) include polyoxyethylene polyol [polyethylene glycol(hereinafter, abbreviated as PEG) etc.], polyoxypropylene polyol[polypropylene glycol (hereinafter, abbreviated as PPG) etc.],polyoxyethylene/propylene polyol, polytetramethylene ether glycol, andEO and/or PO adduct of bisphenols.

Examples of (a2122) include two or more molecules of (a2121) coupledwith alkylene halide (C1 to C6, for example, methylene dichloride).

It is desirable that (a212) has a small unsaturation degree (0.1 meq/gor smaller, preferably 0.05 meq/g or smaller, particularly preferably0.02 meq/g or smaller), and it is desirable that (a212) has a content ofa primary hydroxyl group of at least 30%, preferably at least 50%,particularly preferably at least 70%.

Examples of (a2111) include a product obtained by polydcondensation ofpolycarbonate (c1) to polyol, examples of (a2112) include a productobtained by polyaddition of lactone (c2) to polyol, examples of (a213)include a product obtained by polyaddition of alkylene carbonate (c3) topolyol, and examples of (a2114) include castor oil, and castor oilmodified with polyol or AO.

Examples of polyol constituting them include the aforementioned (a22)and/or (a212)[preferably, having a hydroxyl group equivalent of 500 orsmaller], examples of (c1) include polycarboxylic acids exemplified asthe active hydrogen atom-containing compound [preferably, joint use ofdicarboxylic acid and a small proportion (20% or smaller) of tri- ormore-valent polycarboxylic acid], examples of (c2) include C4 to C12lactone such as 4-butanolide, 5-pentanolide and 6-hexanolide, andexamples of (c3) include C2 to C8 alkylene carbonate such as ethylenecarbonate and propylene carbonate, and these may be used in combinationof two or more.

(a211) can be prepared by the conventional method. (a2111) can beprepared, for example, by a dehydration polycondensation ortransesterification reaction of (c1) or its ester forming derivative[acid anhydride (maleic anhydride, phthalic anhydride), lower alkyl (C1to C4) ester (dimethyl adipate, dimethyl terephthalate etc.), acidhalide (acid chloride etc.)] and an excessive equivalent of polyol, by adehydration polycondensation or transesterification reaction of (c1) orits ester forming derivative and polyol, and thereafter, reaction withAO, or by a reaction of polyol with acid anhydride and AO. (a2112) and(a2113) can be prepared by polyaddition of (c2) or (c3) using polyol asan initiator. A modified castor oil can be prepared bytransesterification of castor oil and polyol and/or AO addition.

Examples of (a2111) include polyethylene adipate diol, polybutyleneadipate diol, polyhexamethylene adipate diol, polyneopentyl adipatediol, polyethylene propylene adipate diol, polyethylene butylene adipatediol, polybutylene hexamethylene adipete diol, polydiethylene adipatediol, poly(polytetramethylene ether)adipate diol, poly(3-methylpentyleneadipate) diol, polyethylene azelate diol, polyethylene sebacate diol,polybutylene azelate diol, polybutylene sebacate diol, polyneopentylterephthalate diol; examples of (a2112) include polycaprolactone diol,polyvalerolactone diol, polycaprolactone triol; examples of (a2113)include polyhexamethylene carbonate diol; examples of (a2112) includecastor oil, trimethylol propane-modified castor oil,pentaerythritol-modified castor oil, and castor oil EO (4 to 30 mole)adduct.

Examples of (a213) include polyalkadiene-based polyol such aspolybutadiene diol [polybutadiene having 1,2-vinyl structure and/or1,4-trans structure (butadiene homopolymer and copolymer such as styrenebutadiene copolymer, acrylonitrile butadiene copolymer) diol], andhydrogenated products thereof (hydrogenation rate: for example, 20 to100%); and copolymers of acrylic-based polyol such as hydroxyalkyl (C2to C6)(meth)acrylate [ethylhydroxyethyl (meth)acrylate] with othermonomer [styrene, alkyl(C1 to C8)(meth)acrylate, etc.]. Examples ofpolybutadiene diol include NISSO-PEG series (G-1000, G-2000, G-3000etc.) (manufactured by Nippon Soda Co., Ltd.), and Poly Bd (R-45M,R-45HT, CS-15, CN-15 etc.) (manufactured by USA ARCO).

Examples of (a214) include a polymer-containing polyol obtained bypolymerizing a radical polymerizable monomer in polyol [theaforementioned (a211) and/or (a212) and, if necessary, (a22)] therein,and examples of a monomer include styrene, (meth)acrylonitrile,(meth)acrylic acid ester, vinyl chloride, and a mixture of two or moreof them. Polymerization of a monomer is usually performed in thepresence of a polymerization initiator. Examples of a polymerizationinitiator include a type which initiates polymerization by producing afree group, for examples, azo compounds such as2,2′-azobisisobutyronitrile (AIBN), and2,2′-azobis-(2,4-dimethylvaleronitrile) (AVN); dibenzoyl peroxide,dicumyl peroxide, and other peroxide, persulfate, perborate, andpersuccinate described in JP-A No. 61-76517. An azo compound,particularly, AIBN and AVN are preferable. An amount of a polymerizationinitiator to be used is usually 0.1 to 20%, preferably 0.2 to 10% basedon a total amount of monomers. Polymerization in polyol may be performedwithout a solvent, but when a polymer concentration is high, it ispreferable to perform the polymerization in the presence of an organicsolvent. Examples of an organic solvent include benzene, toluene,xylene, acetonitrile, ethyl acetate, hexane, heptane, dioxane,N,N-dimethylformamide, N,N-dimethylacetamide, isopropyl alcohol, andn-butanol. If necessary, polymerization can be performed in the presenceof a chain transfer agent (alkylmercaptans, carbon tetrachloride, carbontetrabromide, chloroform, enol ethers described in JP-A No. 55-31880etc.). Polymerization can be performed at a temperature of a degradationtemperature of a polymerization initiator or higher, usually 60 to 180°C., preferably 90 to 160° C., under atmospheric pressure or underpressure, or under reduced pressure. After completion of thepolymerization reaction, the resulting polymer polyol can be used assuch for preparing polyurethane as it is, and it is desirable to removeimpurities such as an organic solvent, a product from degradation of apolymerization initiator, and an unreacted monomer by a conventionalmethod, after completion of the reaction.

(a214) is a translucent or opaque white or claybank dispersion in whichusually 30 to 70% (preferably 40 to 60%, particularly preferably 50 to55%) of a polymerized monomer, that is, a polymer is dispersed inpolyol. A hydroxyl group value of (a214) is usually 10 to 300,preferably 20 to 250, particularly preferably 30 to 200.

A hydroxyl group equivalent of (a21) is usually 150 to 5,000, preferably250 to 3,000, particularly preferably 300 to 2,500.

Among (a2), preferable from a viewpoint of physical property of apolyurethane resin is joint use of (a21) and (a21) as well as a smallproportion (e.g. 20% or smaller) of (a22). Among (a21), preferable is(a212), and particularly preferable is (a211).

As an active hydrogen atom-containing component used in a reaction with(a1), in addition to (a2), other active hydrogen atom-containingcompound (a3) can be used as necessary. Examples of (a3) include anactive hydrogen atom-containing polyfunctional compound (a31) and amonofunctional compound (a32). Examples of (a31) include theaforementioned polyamine, and polyetherpolyamine [hydrogenatedcyanoalkylated (C2 to C4) (cyanoethylated etc.)(a212) and/or (a222)];examples of (a32) include the aforementioned primary monoamine,secondary monoamine such as di-hydrocarbyl(C1 to C20 alkyl, cycloalkyl,aryl and/or aralkyl)amine (dibutylamine etc.) and its AO adduct,monohydric alcohol (C1 to C20 alkanol, cyclohexanol, benzyl alcoholetc.) and its AO adduct.

By using a compound (d) in which at least a part of an active hydrogenatom-containing component comprising polyol (a2) contains a hydrophilicgroup and an active hydrogen atom-containing group in a molecule, aself-emulsification type aqueous polyurethane resin dispersion can beobtained.

Examples of a hydrophilic group in (d) include an anionic group(sulfonic acid group, sulfamic acid group, phosphoric acid group,carboxyl group etc., and salts thereof), a cationic group (quaternaryammonium salt group, primary to tertiary amine salt group, and saltsthereof) and a nonionic group (oxyethylene group, hydroxyl group etc.).Among hydrophilic groups, preferable are a sulfamic acid group, and ahydrophilic group (Q) having the number of groups inherent to an atomicentity by a Davis method of 0.3 or larger. The number of groups inherentto an atomic group by a Davis method is described on page 133 in “NewIntroduction to Surfactant” (manufactured by Sanyo Chemical Industries,Ltd.). Examples of Q include anionic groups such as a sodium salt of acarboxyl group (number of groups=19.1), a potassium salt of a carboxylgroup (number of groups=21.1), and a sodium salt of a sulfonic acidgroup (number of groups-38.7); cationic groups such as a quaternaryammonium salt group, and a tertiary amine acetic acid salt group; andnonionic groups such as an oxyethylene group (number of groups=0.33),and a hydroxyl group (number of groups=0.5).

Examples of (d) include those having 1, or 2 to 8 or more activehydrogen atom-containing groups, and examples of its active hydrogenatom-containing group include a hydroxyl group, a carboxyl group and anamino group. Preferable examples include those having two or more(particularly 2) active hydrogen atom-containing groups, and joint useof this and those having one active hydrogen atom-containing group(weight ratio of joint use is 100/0 to 50/50).

Examples of (d) having an anionic group include sulfonic acid diol[3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid etc.],sulfopolycarboxylic acid [sulfoisophthalic acid, sulfosuccinic acidetc.] and aminosulfonic acid [2-aminoethanesulfonic acid and 3-aminopropanesulfonic acid, etc.]; sulfamic acid diol[N,N-bis(2-hydroxyalkyl)sulfamic acid (C1 to C6 of alkyl group) or itsAO adduct (example of AO includes EO and PO, and an addition mole numberof AOs is 1 to 6): for example, N,N-bis(2-hydroxyethyl)sulfamic acid,N,N-bis(2-hydroxyethyl)sulfamic acid PO 2 mole adduct, etc.];bis(2-hydroxyethyl)phosphate, etc.; dialkylol alkanoic acid [C6 to C24,e.g. 2,2-dimethylol propionic acid (DMPA), 2,2-dimethylol butanoic acid,2,2-dimethylol heptanoic acid, 2,2-dimethylol octanoic acid] and aminoacid (2-aminoethanoic acid etc.); and salts thereof, for example, saltsof amines (triethylamine, alkanolamine, morpholine etc.) and/or alkalimetal salts (sodium salt etc.). Examples of (d) containing a cationicgroup include quaternary ammonium base-containing diol, tertiary aminogroup-containing diol and salts thereof (carboxylic acid salt etc.);examples include alkyl (C1 to C8) dialkanol(C2 to C4)amine(N-methyldiethanolamine etc.) and dialkyl(C1 to C6)alkanol(C2 toC4)amine (N,N-dimethylethanolamine etc.), as well as products obtainedby neutralizing with these acids [organic acids such as C1 to C8carboxylic acid (acetic acid etc.), sulfonic acid (toluenesulfonic acidetc.); inorganic acids such as hydrochloric acid, sulfuric acid,phosphoric acid etc.] and products obtained by quaternarization with aquaternarizing agent [sulfate ester, carbonate ester, and halide havingC1 to C8 alkyl group or benzyl group (dimethyl sulfate, dimethylcarbonate, methyl chloride, benzyl chloride etc.)]. Examples of an ionicgroup (anionic group or cationic group) containing aqueous polyurethaneresin dispersion include those described in JP-B No.42-24192 and JP-BNo.43-9076.

Examples of (d) having a nonionic group include PEG andpolyethylenepropylene glycol (Mn=100 to 3,000). Nonionic (d) and anionic(d) or cationic (d) may be used jointly.

A content of (d) in a self-emulsification type (U) aqueous dispersion ispreferably 0.1% or larger, further preferably 0.5 to 30% based on aweight of a polyurethane resin. In particular, when (d) is a nonioniccompound, a content is preferably 3 to 30% [when (a211) or (a212) isused and a polyoxyethylene chain (addition mole number 2 or larger) iscontained therein, a weight thereof is also included], preferably 5 to20%. A weight of (d) when (d) is an ionic compound is preferably 0.1 to10%, further preferably 0.5 to 5% based on a weight of a polyurethaneresin. When this is converted into equivalent, a weight is preferably0.01 to 2 meq/g, further preferably 0.05 to 1 meq/g.

A self-emulsification type (U) aqueous dispersion can be prepared, forexample, by charging an H component comprising (a1), (a2) containing (d)and, if necessary, a terminating agent (e1) and, if necessary, anorganic solvent, forming a urethane prepolymer at one stage or amultiple stage, then, after the prepolymer is hydrophilized (neutralizedor quaternarized), or while hydrophilizing, mixing the prepolymer withan aqueous medium, if necessary, containing a chain extender (f), acrosslinking agent (x) and/or a terminating agent (e2) to obtain anaqueous dispersion, and performing a reaction [chain extension withwater or (f) and, if necessary, crosslinking with (x) and/or reactiontermination with (e2)] until a NCO group is substantially consumed.Hydrophilization (neutralization or quaternarization) may be performedafter formation of an aqueous dispersion. When chain extension with (f)and, if necessary, reaction termination with (x) and/or (e2) areperformed, it is preferable that a prepolymer is dispersed in an aqueousmedium and, thereafter, (f) and, if necessary, (x) and/or (e2) are addedto react with a prepolymer.

Alternatively, a (U) aqueous dispersion may be formed by reacting (a1)and the aforementioned H component in the presence of an organic solventto form a prepolymer solution, and reacting with a chain extender (f)and, if necessary, a crosslinking agent (x) and/or a terminating agent(e2), or by reacting (a1) and the aforementioned H component and, ifnecessary, a crosslinking (x) and/or a terminating agent (e2) in thepresence of an organic solvent, at one stage, whereby, a solution of (U)in an organic solvent is formed, and is dispersed in an aqueous medium.Also in this case, hydrophilization (neutralization or quaternarization)may be performed before formation of an aqueous dispersion, during astage of formation, or after formation.

A prepolymer is formed by reacting (a1) and an H component at such aproportion that an equivalent ratio of an isocyanate group/an activehydrogen-containing group (except for carboxyl group) is usually 1.01 to2, preferably 1.1 to 1.6. An amount of (e1) which is added to an Hcomponent as necessary is usually 5% by equivalent or smaller,preferably 3% by equivalent or smaller. Formation of a prepolymer isperformed by a reaction at usually 20° C. to 150° C., preferably 60° C.to 110° C., and a reaction time is 2 to 10 hours. Formation of aprepolymer can be performed in the presence or the absence of an organicsolvent which is substantially unreactive with a NCO group. A prepolymerhas a free NCO group content of usually 0.5 to 5%. Hydrophilization of aprepolymer can be performed using a base [when (d) is anionic compound]or an acid or a quaternarizing agent [when (d) is cationic compound]. Anaqueous dispersion can be formed by mixing and dispersing a prepolymerwith an aqueous medium [water or a mixture of water and a hydrophilicorganic solvent, if necessary, containing (f), (x) and/or (e)] atusually 10° C. to 60° C., preferably 20° C. to 40° C., to react them,and distilling off the organic solvent as necessary.

Examples of an organic solvent used upon the aforementioned reaction,and a hydrophilic solvent to be contained in an aqueous medium includesolvents which are substantially unreactive with a NCO group, andhydrophilic (water-miscible) solvents (ketones, esters, ethers, amides,alcohols), respectively, among organic solvents exemplified above(a214). A ratio of water and a hydrophilic solvent is usually 100/0 to50/50, preferably 100/0 to 80/20, particularly preferably 100/0.

As a chain extender (f) and a crosslinking agent (x), polyamines [(h32)as described above] can be used. Amounts of (f) and (x) to be used issuch an amount that primary and secondary amino groups of (f) and (x)are usually 0.5 to 2 equivalent, preferably 0.9 to 1.2 equivalentrelative to 1 equivalent of an isocyanate group remaining in aprepolymer. Examples of a terminating agent (e1) include monofunctionalcompounds [(a32) as described above: primary monoamine, secondarymonoamine, monohydric alcohol, and monofunctional compounds among (d)];examples of a terminating agent (e2) include the aforementionedmonofunctional compounds, and [(h312) as described above: mono- anddi-alkanolamine, etc.]. An amount of (e2) to be used is usually 0.5equivalent or smaller, preferably 0.03 to 0.3 equivalent relative to 1equivalent of a free NCO group of a prepolymer. (e2) may be contained inan aqueous medium, or may be added at a stage of chain extension of aprepolymer.

By using (d) as at least a part of (e1) and/or (e2), in place of or inaddition to use of (d) as at least a part of (a2), a self-emulsificationtype (U) aqueous dispersion may be prepared.

A (U) aqueous dispersion may be converted into an emulsifier-emulsifiedtype (U) aqueous dispersion using an emulsifier.

An emulsifier-emulsified type (U) aqueous dispersion can be prepared byforming a prepolymer in the presence or the absence of an organicsolvent, mixing the prepolymer with an aqueous medium to obtain anaqueous dispersion, performing a reaction [chain extension and, ifnecessary, crosslinking and/or reaction termination], and distilling anorganic solvent off, if necessary, according to the same manner as thatdescribed above except that an emulsifier is used, in place of, inaddition to use of (d) as at least a part of (a2) [or (e1) and/or (e2)].

An emulsifier may be added to either or both of a prepolymer and anaqueous medium. When an emulsifier is reactive with a prepolymer, it ispreferable to add the emulsifier to an aqueous medium. An amount of anemulsifier to be added is usually 0.2 to 10%, preferably 0.3 to 6% basedon a weight of a urethane prepolymer. When (d) is used, the amount maybe an amount smaller than the aforementioned range, depending on anamount of (d).

Examples of an emulsifier include anionic, cationic, nonionic andamphoteric surfactants, polymer-type emulsification dispersant, andjoint use of two or more of them, for example, those described in U.S.Pat. No. 3,929,678 and U.S. Pat. No. 4,331,447.

Examples of an anionic surfactant include ether carboxylic acid having aC8 to C24 hydrocarbon group or a salt thereof [lauryl ether sodiumacetate, (poly)oxyethylene [polymerization degree (hereinafter,abbreviated as p)=1 to 100] lauryl ether sodium acetate etc.], sulfateester or ether sulfate ester having a C8 to C24 hydrocarbon group andsalts thereof [sodium laurylsulfate, (poly)oxyethylene (p=1 to 100)sodium laurylsulfate, (poly)oxyethylene (p=1 to 100) laurylsulfatetriethanolamine, (poly)oxyethylene (p=1 to 100) palm oil fatty acidmonoethanolamide sodium sulfate etc.], sulfonate salt having a C8 to C24hydrocarbon group [sodium dodecylbenzenesulfonate etc.], sulfosuccinatesalt having one or two C8 to C24 hydrocarbon group(s), phosphate esteror ether phosphate ester having a C8 to C24 hydrocarbon group, and saltsthereof [sodium laurylphosphate, (poly)oxyethylene (p=1 to 100) sodiumlauryletherphosphate etc.], fatty acid salt having a C8 to C24hydrocarbon group [sodium laurate, lauric acid triethanolamine etc.] andacylated amino acid salt having a C8 to C24 hydrocarbon group [sodiumpalm oil fatty acid methyltaurine, sodium palm oil fatty acid sarcosine,palm oil fatty acid sarcosine triethanolamine, N-palm oil fatty acidacyl-L-glutamic acid triethanolamine, sodium N-palm oil fatty acidacyl-L-glutamate, lauroylmethyl-β-alanine sodium etc.]; examples of anonionic surfactant include aliphatic alcohol (C8 to C24)AO(C2 to C8)adduct (p=1 to 100), polyhydric (dihydric to decahydric or more-hydric)alcohol fatty acid (C8 to C24)ester [GL monostearate, sorbitanmonolaurate etc.], fatty acid (C8 to C24)alkanolamide [1:1 type palm oilfatty acid diethanolamide, 1:1 type lauric acid diethanolamide etc.],(poly)oxyalkylene(C2 to C8, p=1 to 100)alkyl(C1 to C22)phenylether,(poly)oxyalkylene(C2 to C8, p=1 to 100)alkyl(C8 to C24)amine andalkyl(C8 to C24)dialkyl(C1 to C6)amine oxide (lauryldimethylamine oxideetc.); examples of a cationic surfactant include quaternary ammoniumsalt type [stearyltrimethylammonium chloride, behenyltrimethylammoniumchloride, distearyldimethylammonium chloride, ethyl sulfate lanolinfatty acid aminopropylethyldimethylammonium etc.], amine salt type[stearic acid diethylaminoethylamide lactate, dilaurylaminehydrochloride, oleylamine lactate etc.]; examples of an amphotericsurfactant include betaine type amphoteric surfactant [palm oil fattyacid amidopropyldimethylaminoacetic acid betaine,lauryldimethylaminoacetic acid betaine,2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine,laurylhydroxysulfobetaine,lauroylamidoethylhydroxyethylcarboxymethylbetaine sodiumhydroxypropylphosphate etc.], and amino acid amphoteric surfactant[sodium β-laurylaminopropionate etc.].

Examples of a polymer-type emulsification dispersant include polyvinylalcohol, starch and a derivative thereof, cellulose derivative such ascarboxymethylcellulose, methylcellulose and hydroxyethylcellulose,carboxyl group-containing (co)polymer having Mn=1,000 to 50,000 such assodium polyacrylate, and polymer-type dispersants having a urethane bondor an ester bond described in U.S. Pat. No. 5,906,704 [e.g. dispersantin which polycaprolactonepolyol (a2112) and polyetherdiol (a2121) arelinked with polyisocyanate (a1)] can be used.

Among these emulsifiers, preferable are a nonionic surfactant and apolymer-type emulsification dispersant, in particular, a polymer-typeemulsification dispersant having a urethane bond or an ester bonddescribed in the aforementioned gazette.

A weight average particle diameter of the (U) aqueous dispersion in thepresent invention is usually 0.01 to 4 μm, preferably 0.01 to 3 μm.

In the aforementioned urethanating reaction, in order to promote thereaction, a catalyst which is used in a normal urethanating reaction maybe used, if necessary. Examples of the catalyst include an amine-basedcatalyst such as triethylamine, N-ethylmorpholine, triethylenediamine,and cycloamidines [1,8-diaza-bicyclo(5,4,0)undecene-7 (manufactured bySan apro LTD., DBU) etc.] described in U.S. Pat. No. 4,524,104; tinsystem catalysts such as dibutyltin dilaurate, dioctyltin dilaurate andtin octylate; titanium system catalysts such as tetrabutyl titanate.

An apparatus for emulsification-dispersing a solution of a prepolymer or(U) in an aqueous medium is not particularly limited, but the followingformat emulsifiers are exemplified: 1) anchor agitator type, 2) rotatorstator type [e.g. “Ebara Milder” (manufactured by Ebara Corporation)],3) line mill type [e.g. line flow mixer], 4) static tube mixing type[e.g. static mixer], 5) vibration type [e.g. “VIBRO MIXER” (manufacturedby Reika Kogyo)], 6) ultrasonic shock type [e.g. ultrasoundhomogenizer], 7) high pressure impact type [e.g. Gaulin homogenizer(Gaulin)], 8) membrane emulsification type [e.g. membrane emulsificationmodule], and 9) centrifugation thin layer contact type [e.g. fill mix].Among them, preferable are 5), 8) and 9).

When chain extension with (f) and, if necessary, crosslinking with (x)and/or reaction termination with (e2) are performed, it is preferable todisperse a prepolymer in an aqueous medium using a continuous typeemulsifier [preferably, the aforementioned 2), e.g., Ebara Milder], andadding (f), if necessary, (x) and/or (e2) to mix them using a batch typeemulsifier [preferably, the aforementioned 1)] anchor-agitator type], toreact with a prepolymer.

Mn of (U) is usually 2,000 to 2,000,000 or larger, preferably 10,000 to1,500,000, particularly preferably 100,000 to 500,000 in the case ofnon-crosslinked (thermoplastic) (U). Crosslinked (U) may have Mn higherthan the aforementioned range, or Mn which is too high to be measured byGPC.

Examples of a process for preparing aqueous dispersions (I) and (II) ofa resin having at least two peaks in a particle diameter distributioncurve of the present invention include I) a method of separatelypreparing an aqueous dispersion of a resin (A1) and an aqueousdispersion of other resin (A2) having two or more different particlediameters, and then mixing them; II) a method of dispersing a solutionor a melt of other resin (A2) or a precursor of (A2p) in an aqueousdispersion of a resin (A1) and, in the case of (A2p), further convertinginto (A2), to prepare a dispersion containing particles comprising (A2)having a different particle diameter from that of (A1) III) a method ofdispersions having two or more different particle diameters at the sametime; and IV) a method of a combination of two or more of theaforementioned I) to III). From a viewpoint of productivity, preferableare I), IV) and, in particular, II).

In the method of II), examples of a combination of (A1) and (A2) or aprecursor thereof include the case where (A1) is (U), (E), (M) or (D),and (A2p) is a urethane prepolymer, and the case where (A1) is (U), (E),(M) or (D), and (A2) is (E). Among them, preferable is the case where(A1) is (U), (E) or (M), and (A2p) is a urethane prepolymer (U2p), inparticular, the case where (A1) is (U), and (A2p) is (U2p).

Processes for preparing aqueous dispersions (I) and (II) may be batchmanner or continuous manner. From a viewpoint of productivity,preferable is continuous manner. Preparation of a dispersion of a resin(A1) and the aforementioned method of II) may be performed in acontinuous manner; it is preferable to continuously disperse a precursor(Alp) of a resin (A1) in an aqueous medium to form a dispersion of(Alp), mixing this with (f), if necessary, (x) and/or (e2) in a batchmanner to react them, to form a dispersion of (A1), and continuouslydisperse a solution or a melt of (A2) or (A2p) therein according to theaforementioned method II).

Aqueous dispersions (I) and (II) of (U) can be prepared by preparing anaqueous dispersion of a polyurethane resin (U1) in advance by theaforementioned self-emulsification type or emulsifier emulsified typemethod, according to the aforementioned method of II), thereafterintroducing a liquid (melt or solution-like) urethane prepolymer (U2p)using an emulsifying machine in the state where the aqueous dispersionis flown or stirred, to disperse it and, at the same time, orthereafter, performing a chain extension reaction with water, or adding(f) to perform a chain extension reaction, to convert (U2p) into apolyurethane resin (U2).

It is preferable that an aqueous dispersion of (U1) is such that (F) isadded to an aqueous dispersion of a precursor of (U1) (U1p), and (U1p)is chain-extended. When (U1p) is chain-extended, a standard deviation, askewness and a kurtosis of a peak of the aforementioned particlediameter distribution curve are easily in preferable ranges. In thiscase, although a chain extension reaction may be performed by either ofa continuous reaction apparatus or a batch reaction apparatus, it ispreferable to perform the reaction by a batch reaction apparatus from aviewpoint of easy completion of the reaction.

Alternatively, (U2) may be formed by adding (f) to an aqueous dispersionof (U1) in advance, dispersing (U2p), and performing chain extension atthe same time with dispersing of (U2p).

As an emulsification dispersing apparatus, any of the aforementionedvibration type, membrane emulsification type and centrifugation thinmembrane contact type may be used.

When a solution of a resin or a precursor is used, an organic solventmay be distilled off as necessary.

When a resin (A) is (U), examples of means to make the aforementioned(U2p) a dispersion of (U2) having a different particle diameter fromthat of an aqueous dispersion of (U1) [e.g., (U2) has a larger particlediameter] include 1) when (U2p) is a self-emulsification type urethaneprepolymer, reduction in an amount of its hydrophilic group [amount of(d)]; 2) when (U2p) is an emulsifier-emulsified urethane polymer,reduction in an amount of an emulsifier to be added; 3) when adispersion of (U2) or (U2p) contains a hydrophilic organic solvent,reduction in a content thereof; 4) reduction in a shear force atemulsification of a urethane prepolymer; and a combination of two ormore of them.

An amount of (d) in (U2p) in the case of 1) is preferably 20% orsmaller, further preferably 10% or smaller, particularly preferably 5%or smaller, based on a weight of (U2p), and is preferably 70% orsmaller, particularly 50% or smaller of a content of (d) in (U1). Anamount of an emulsifier to be added in the case of 2) is preferably 6%or smaller, particularly preferably 0.2 to 5% based on a weight of(U2p), and preferably 70% or smaller, particularly 50% or smaller of anamount of an emulsifier to be added in an aqueous dispersion of (U1). Inthe case of 3), an amount of a hydrophilic organic solvent to be addedis preferably 10% or smaller, particularly preferably 0.3 to 8% based ona weight of (U2) or (U2p), and preferably 70% or smaller, particularly50% or smaller of an amount of a hydrophilic organic solvent to be addedin an aqueous dispersion of (U1).

In aqueous dispersions (I) and (II) of (U), any of at least two particlediameters may be larger, but it is preferable that a particle diameterof a particle formed from a liquid urethane prepolymer is larger, from aviewpoint of easy preparation.

Examples of a polyaddition type resin include, besides (U), apolythiourethane resin such as a polyaddition product ofpolyisothiocyanate [compound corresponding to the aforementioned (a1)(inwhich NCO group is substituted with NCS group)] and an H componentcomprising polyol [aforementioned (a2)]; a poly(thio)urea resin such asa polyaddition product of polyamine [aforementioned (h32) and/or (a312)]and polyiso(thio)cyanate (aforementioned (a1) and/or aforementionedpolyisothiocyanate); polymethylenemalonamide such as a polyadditionproduct of diketene and polymethylenediamine, a polyaddition product ofdithiol [aforementioned (h6) such as hexamethylenedithiol] and a divinylcompound (alkadiene, dicarboxylic acid divinyl ester etc. describedbelow).

A process for preparing aqueous dispersions of these polyaddition typeresins, a preferable content of (d) in a self emulsification type resinand an amount of an emulsifier to be used in an aqueous dispersion of anemulsifier-emulsified type resin, a weight average molecular diameter ofan aqueous dispersion of a resin, Mw of a resin, and processes forpreparing aqueous dispersions (I) and (II) are the same as thosedescribed in (U).

A resin (E) includes a polycondensate of polyols and polycarboxylic acidand a polycondensate of oxycarboxylic acid, and the latter includespolylactone.

Examples of polyols include the aforementioned (a22) and/or (a212).Preferable is joint use of an aliphatic dihydric to tetrahydric alcoholand two or more of these, and further preferable is joint use of adihydric alcohol (in particular, at least one kind selected from NPG,BEPD and HD) and a trihydric alcohol and/or tetrahydric alcohol(particularly, TMP and/or PE). From a viewpoint of a hardness of theresulting coated film and a viscosity of a paint, a ratio of both ofthem is preferably 99.5/0.5 to 70/30, particularly 98/2 to 80/20.

Examples of polycarboxylic acid include the aforementioned (h4).Preferable are C2 to C10 aliphatic dicarboxylic acid, C8 to C18 aromaticdicarboxylic acid, C9 to C18 trivalent to tetravalent or more-valentaromatic polycarboxylic acid, and joint use of two or more of them.Further preferable are aliphatic dicarboxylic acid (particularly, adipicacid and/or sebacic acid), aromatic divalent to tetravalent carboxylicacid (particularly, at least one selected from isophthalic acid,terephthalic acid and trimellitic acid) and, particularly, joint use ofthem (ratio 20/80 to 50/50).

Examples of oxycarboxylic acid include C4 to C12 hydroxyalkanoic acid,for example, acid corresponding to the aforementioned (c2).

(E) can be prepared by the conventional polyester forming method, forexample, by esterifying or transesterifying polyols and polycarboxylicacid or its ester forming derivative [e.g. acid anhydride, loweralkyl(C1 to C4)ester etc.], by polycondensing oxycarboxylic acid, or byreacting an initiator (oxycarboxylic acid, polyols and/or polycarboxylicacid, or its partial polycondensate) with (c2) (e.g. ε-caprolactone) oracid anhydride and AO.

Esterification or transesterification can be performed at a reactiontemperature of usually 100 to 250° C., if necessary, using a catalystand/or a solvent. As a catalyst and a solvent, those which areconventionally used in a polyesterification reaction can be used.Examples of a catalyst include dibutyltin dilaurate, tin octylate,p-toluenesulfonic acid, and lithium naphthenate; examples of a solventinclude aromatic hydrocarbons and ketones exemplified in theaforementioned (a214).

A process for preparing an aqueous dispersion of (E) is not particularlylimited. An aqueous dispersion of an emulsifier-emulsified type (E) canbe prepared by the same process as that for preparing an aqueousdispersion of the aforementioned emulsifier-emulsified type (U) usingthe same emulsifier. In addition, an aqueous dispersion ofself-emulsification type (E) can be prepared by using jointly a compoundhaving a hydroxy group as an active hydrogen atom-containing group (PEG,EO adduct of bisphenol A, dialkylolalkanoic acid, sulfonic acid diol)among the aforementioned (d) as at least a part of polyols.Alternatively, it can be prepared by using jointly, for example,polycarboxylic acid (d1) having an anionic group other than a carboxylgroup [e.g. sulfoisophthalic acid (salt) and its ester formingderivative] as polycarboxylic acids.

A preferable content of (d) in self-emulsification type (E) and anamount of an emulsifier to be used in an aqueous dispersion ofemulsifier-emulsified type (E) are the same as those in (U).

A weight average particle diameter of the aqueous dispersion of (E)obtained in these methods is usually 0.01 to 4 μm, preferably 0.01 to 3μm. Mw of (E) is usually 2,000 to 2,000,000 or larger, preferably 10,000to 1,500,000.

Aqueous dispersions (I) and (II) of (E) can be prepared by preparing anaqueous dispersion of a polyester resin (E1) in advance by theaforementioned emulsifier-emulsified type or self-emulsification typemethod, according to the aforementioned method of II), and thenintroducing a solution-like or melt-like polyester resin (E3) of asolution of an aqueous dispersion of (E1) in the state where the aqueousdispersion is flown or stirred by using emulsifying machine, to dispersetherein.

In this case, in order that (E2) is a dispersion having a differentaverage particle diameter from that of an aqueous dispersion of (E1)[e.g. (E2) has a larger particle diameter], a method of reducing anamount of (d), an emulsifier and/or a hydrophilic solvent is used as inthe case of an aqueous dispersion of (U).

Examples of a polyamide resin include a polycondensate of polyamine andpolycarboxylic acid, a polycondensate of aminocarboxylic acid, andpolyesterpolyamide obtained by copolycondensing a polyamide formingcomponent (polyamine and polycarboxylic acid or aminocarboxylic acid)and polyols.

Examples of polyamine include the aforementioned (h32) and/or (a312).Preferable is diamine, in particular, hexamethylenediamine.

Examples of polycarboxylic acid include the aforementioned (h4).Preferable are C2 to C10 aliphatic dicarboxylic acid, C8 to C18 aromaticdicarboxylic acid, C9 to C18 trivalent to tetravalent or more-valentaromatic polycarboxylic acid, and joint use of two or more of them, andfurther preferable are aliphatic dicarboxylic acid (particularly, adipicacid and/or sebacic acid), and aromatic dicarboxylic acid (particularly,isophthalic acid and/or terephthalic acid).

Examples of aminocarboxylic acid include C4 to C 12 aminoalkanoic acidsuch as ω-capronamino acid, ω-aminoenanthic acid, ω-aminocaprylic acid,ω-aminopelargonic acid, ω-aminocapric acid, ω-aminoundecanoic acid and12-aminododecanoic acid.

As polyols, used for forming polyesterpolyamide, the aforementioned(a22) and/or (a212) can be used.

Polyamide can be prepared by the conventional polyamide forming method,for example, by polycondensation of polyamine and polycarboxylic acid,by polycondensation of aminocarboxylic acid, or by reacting an initiator(aminocarboxylic acid, polyamine and/or polycarboxylic acid, or itspartial polycondensate) with lactam (e.g. at least one of caprolactam,enanthlactam, capril lactam, and laurolactam).

Polyesterpolyamide can be prepared, for example, by a method ofcopolycondensing polyols in addition to the aforementioned polyamideforming component, to introduce an ester bond, or by a method ofreacting carboxyl group (or its ester forming derivativegroup)-containing polyamide and polyols.

A process for preparing an aqueous dispersion of polyamide is notparticularly limited. An aqueous dispersion of an emulsifier-emulsifiedtype polyamide can be prepared by the same process as that for preparingan aqueous dispersion of the aforementioned emulsifier-emulsified type(U) using the same emulsifier. An aqueous dispersion ofself-emulsification type polyamide can be prepared by using, as at leasta part of polyamine and/or polycarboxylic acid, (d) having amino groupas an active hydrogen atom-containing group among the aforementioned (d)[such as bis(3-aminopropyl)methylamine, 3,4-diaminobenzoic acid,diaminotoluenesulfonic acid, a salt thereof, polyoxyethylenechain-containing polyamine (diaminoethyl ether of PEG etc.)], andpolycarboxylic acid (d1) having an anionic group other than a carboxylicgroup [e.g. sulfoisophthalic acid (salt) and its ester formingderivative]. In addition, an aqueous dispersion of self-emulsificationtype polyesterpolyamide can be prepared by using (d) having a hydroxylgroup as an active hydrogen atom-containing group among (d) (PEG, EOadduct of bisphenol A, dialkylolalkanoic acid, sulfonic acid diol etc.),and reacting this with a polyamide forming component or carboxyl group(or its ester forming derivative group)-containing polyamide.

A preferable content of (d) in self-emulsification-type polyamide, anamount of an emulsifier to be used in an aqueous dispersion ofemulsifier-emulsified type polyamide, a weight average moleculardiameter of an aqueous dispersion of polyamide, Mw of polyamide, andprocesses for preparing aqueous dispersions (I) and (II) are the same asthose in (E).

Examples of a polycondensation type resin include, besides theaforementioned polycondensation type resins, a silicone resin; apolycarbonate resin; a polyimide resin such as a polycondensate ofpyromellitic dianhydride and diamine [aforementioned (h32):hexamethylenediamine, nonamethylenediamine etc.]; a polybenzimidazoleresin such as a polycondensate of tetraaminobiphenyl and dicarboxylicacid [aforementioned (h4): sebacic acid etc.]; a polyurea resin such asa polycondensate of urea and diamine [aforementioned (h32)]; apolysulfonamide resin such as a polycondensate ofbenzyldisulfonylchloride and diamine [aforementioned (h32):hexamethylenediamine etc.]; a polysulfonate copolymer such as apolycondensate of bisphenols (bisphenol A etc.) and two kinds ofaromatic disulfonyl chlorides (one kind may be carboxylic acidchloride); a polysulfone resin such as a polycondensate of bisphenols(bisphenol A etc.) and dichiorodiphenylsulfone; a polysulfide resin suchas a polycondensate of sodium polysulfide and dichloro compound(ethylene dichloride, ethylene ether dichloride); a poly-p-phenyleneresin.

Examples of a silicone resin include organopolysiloxane such aspolydimethylsiloxane, polymethylphenylsiloxane, methylstyrene-modifiedsilicone, olefin-modified silicone, fluorine-modified silicone, andhydrophilic group-modified silicone (polyether-modified silicone,alcohol-modified silicone, amino-modified silicone, mercapto-modifiedsilicone, epoxy-modified silicone, carboxyl-modified silicone, etc.).

Examples of a polycarbonate resin include polycarbonate resinssynthesized [prepared by a reaction with alkylene carbonate (c3)(polyaddition and transesterification), transesterification withdiphenyl carbonate, or phosgenization] from a dihydroxyl compound [e.g.aforementioned (a221) divalent alcohol, aforementioned (h2) divalentphenol, and AO adduct thereof]. Specific examples include polycarbonatessynthesized from bisphenols such as 4,4′-dihydroxydiaryl(cyclo)alkaneand the alkane substituted with a halogen [bisphenol A,4,4′-dihydroxydiphenyl-2,2-butane,4,4′-dihydroxydiphenyl-2,2-(4-methyl)pentane,4,4′-dihydroxydiphenyl-1,1-cyclohexane,4,4′-dilhydroxy-3,3′,5,5′-tetrachlorodiphenyl-2,2-propane etc.].Preferable is polycarbonate of bisphenol A.

A process for preparing aqueous dispersions of these polycondensationsystem resins, a preferable content of (d) in a self-emulsification-typeresin, an amount of an emulsifier to be used in an aqueous dispersion ofan emulsifier-emulsified type resin, a weight average particle diameterof an aqueous dispersion of a resin, Mw of a resin, and processes forpreparing aqueous dispersions (I) and (II) are the same as those in (E).

Examples of an addition condensation type resin include a phenol resinsuch as a condensate of phenols [phenol, cresol, xylenol, alkyl (C2 toC10) phenol, p-chlorophenol etc.] and formaldehyde (novolak and resol);and an amino resin such as a condensate of an amino group -containingcompound [(thio)urea, ethyleneurea, melamine, dicyandiamide,benzoguanamine, aniline, toluenesulfonamide etc.] and formaldehyde (urearesin, melamine resin etc.). Mw of them is usually 2,000 to 2,000,000 orlarger, preferably at least 10,000.

Examples of an epoxy-based resin include epoxy-based resins described inBritish Patent No. 1543099, U.S. Pat. Nos. 5238767 and 5162437, and“Epoxy Resins” (published by McGraw-Hill in 1957), a glycidyl type epoxyresin (diglycidyl ether of bisphenol A etc.) and a non-glycidyl typeepoxy resin (alicyclic epoxy resin etc.). Mw of an epoxy resin isusually 100 to 10,000 or larger, preferably 200 to 5,000, and an epoxyequivalent is usually 50 to 5,000 or larger, preferably 200 to 2,500. Anepoxy resin can be cured by the normally used curing agent such aspolyamine [aforementioned (h32)], polycarboxylic acid(anhydride)[aforementioned (h4), or its anhydride] or the like. Mw of acured product is usually 2,000 to 2,000,000 or larger, preferably atleast 10,000.

A process for preparing an aqueous dispersion of these resins, apreferable content of (d) in a self-emulsification-type resin, an amountof an emulsifier to be used in an aqueous dispersion of anemulsifier-emulsified type resin, a weight average particle diameter ofan aqueous dispersion of a resin, and processes for preparing aqueousdispersions (I) and (II) are the same as those in (U). An epoxy resinmay be cured upon formation of an aqueous dispersion or after formation,or a pre-cured epoxy resin may be dispersed in an aqueous medium, andparticles comprising a cured epoxy resin (A2) having a differentparticle diameter from that of (A1) can be prepared by dispersing usingan epoxy resin as a precursor (A2p) by the aforementioned method of II),and curing the dispersion with a curing agent.

The aqueous dispersions [(I) and (II)] of the present invention include,in addition to aqueous dispersions having different particle diameterscomprising the same type resins as described above, aqueous dispersionscomprising at least two different type resins selected from the groupconsisting of a polyaddition type resin, a polycondensation type resin,an addition condensation type resin and a ring-opening-polymerizationtype resin [e.g. a combination of (U) and (E) and/or polyamide resinand/or phenol resin, a combination of (E) and polyamide resin and/orphenol resin]. These aqueous dispersions can be prepared by any of theaforementioned I) to IV) methods.

In addition, the aqueous dispersions [(I) and (II)] of the presentinvention include aqueous dispersions comprising particles of at leastone resin selected from the group consisting of a polyaddition typeresin, a polycondensation type resin, an addition condensation typeresin and a ring-opening-polymerization type resin, and particles of atleast one resin selected from the group consisting of additionpolymerization type resins [vinyl-based resin (V)].

Examples of the resin (V) include one or more (co)polymer(s) ofpolymerizable unsaturated monomer(s). The polymerizable unsaturatedmonomer includes the following:

(1) (Meth)acrylic Acid Ester

(1-1) Hydrocarbyl(C1 to C20) (meth)acrylate such as (cyclo)alkyl(meth)acrylate [methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl,2-ethylhexyl and lauryl (meth)acrylates etc.], and aromaticring-containing (meth)acrylate [benzyl (meth)acrylate etc.];

(1-2) Hydroxy group and/or ether bond-containing(meth)acrylate:(meth)acrylate of polyol [aforementioned (a22) and/or(a212), preferably having a hydroxyl group equivalent of 600 or smaller]such as mono(meth)acrylate of diol [C2 to C12 aliphatic dihydricalcohol, its AO adduct (addition mole number 1 to 20) and dihydricphenol AO adduct (addition mole number 2 to 20) such as EG, PEG (p=2 to20), PPG (p=2 to 20) and bisphenol A EO adduct], and mono(meth)acrylateof trihydric to octahydric or more-hydric polyol [aliphatic polyhydricalcohol (GL, TMP, PE, sorbitol etc.), its AO adduct (addition molenumber 1 to 20) etc.]; (meth)acrylate of hydrocarbyl(C1 to C20)ether ofthe aforementioned polyol, such as methoxyPEG (meth)acrylate; carboxylicacid [C1 to C30 monocarboxylic acid such as aliphatic monocarboxylicacid (formic acid, acetic acid, oleic acid, acetoacetic acid etc.),alicyclic monocarboxylic acid (cyclohexanecarboxylic acid, abietic acidetc.), aromatic monocarboxylic acid in which a nucleus may besubstituted (substitution degree 1 to 3) with an alkyl group (C1 to C10)and/or halogen (Cl, Br etc.) (benzoic acid, toluic acid,xylenecarboxylic acid, 4-butylbenzoic acid, 2-methyl-4-chlorobenzoicacid, nonylbenzoic acid etc.)] ester of mono(meth)acrylate of theaforementioned polyol [mono(meth)acrylate of dihydric alcohol etc.],such as (meth)acryloyloxyethyl and (meth)acryloyloxypropylacetylacetate; and polyfunctional (meth)acrylate, such as poly(meth)acrylateof the aforementioned polyol [di(meth)acrylate of dihydric alcoholetc.];

(1-3) Cationic group (amino group or quaternary ammoniumbase)-containing (meth)acrylate: primary to tertiary aminogroup-containing (meth)acrylate, such as amino(hydroxyl)alkyl(C2 to C4)(meth)acrylate [aminoethyl, aminopropyl and 3-amino-2-hydroxy-propyl(meth)acrylate etc.], (di)alkyl(C1 to C4)aminoalkyl (C2 to C4) (meth)acrylate [(di) methylaminoethyl, (di)ethylaminoethyl,(di)methylaminopropyl and 3-(di)methylamino-2-hydroxy-propyl(meth)acrylate], and heterocyclic amino-containing (meth)acrylate[morpholinoalkyl(C2 to C4) (meth)acrylate such as morpholinoethyl(meth)acrylate, piperidinoalkyl(C2 to C4) such as piperidinoethyl(meth)acrylate etc.]; products obtained by neutralizing orquaternarizing them [products obtained by neutralizing or quaternarizingwith acids or quaternarizing agents exemplified in (d) containing theaforementioned cationic group], such as(meth)acryloyloxyethyltrialkyl(C1 to C4)ammonium salts (chloride,methsulfate, acetate etc.); and

(1-4) Anionic group (carboxyl group or sulfo group)-containing(meth)acrylate, such as lactone (C3 to C12) adduct (addition mole number1 to 10) of (meth)acrylic acid [ε-caprolactone 1 to 5 mole adduct of(meth)acrylic acid] and sulfoalkyl(C2 to C4) (meth)acrylate [sulfopropyl(meth)acrylate etc.]; a salt thereof such as a salt of amines(triethylamine, alkanolamine, morpholine etc.) and/or alkali metal salt(sodium etc.);

(2) Carboxyl group-containing monomer: unsaturated monocarboxylic acidsuch as (meth)acrylic acid, (iso)crotonic acid and cinnamic acid;unsaturated dicarboxylic acid such as maleic acid, fumaric acid,itaconic acid, citraconic acid and mesaconic acid; monoalkyl(C1 toC20)ester of unsaturated dicarboxylic acid, such as maleic acidmonomethyl ester, maleic acid monoethyl ester and itaconic acidmonobutyl ester; unsaturated carboxylic anhydride, such as maleicanhydride and itaconic anhydride; salts of these unsaturated carboxylicacids such as the same salts as those of the aforementioned (1-4);

(3) Amide group-containing monomer: (meth)acrylamide; N-hydroxyalkyl orhydrocarbyl(C1 to C20)-substituted (meth)acrylamide, such asN-methylol(meth)acrylamide, N-alkyl and N, N-dialkyl(meth)acrylamide[N-butyl(meth)acrylamide etc.], (meth)acrylformamide,N-methyl-N-vinylacetamide, methyl α-acetoaminoacrylate,N-vinylpyrrolidone; cationic group (amino group or quaternary ammoniumsalt group)-containing (meth)acrylamide, such as (meth)acrylamidecorresponding to the aforementioned (1-3)[(meth)acrylamidoethyltrialkyl(C1 to C4)ammonium salt etc.]; anionicgroup (carboxyl group or sulfo group)-containing (meth)acrylamide, suchas (meth)acrylamidoalkyl(C2 to C4)sulfonic acid[(meth)acrylamidopropylsulfonic acid etc.], lactam(C3 to C12) adduct(addition mole number 1 to 10) of (meth)acrylic acid [ε-caprolactam 1 to5 mole adduct of (meth)acrylic acid etc.], salts thereof such as thesame salts as those of the aforementioned (1-4); polyfunctional(meth)acrylamide, such as methylenebis(meth)acrylamide;

(4) Aromatic unsaturated hydrocarbon: styrene-based monomer, such as ST,hydrocarbyl-substituted ST (α- and o-methylST, vinyltoluene, ethylST,dimethylST, isopropylST, butylST, phenylST, cyclohexylST, benzylST,α-methylSTdimer etc.), crotylbenzene, vinylnaphthalene and indene, aswell as polyfunctional aromatic unsaturated hydrocarbon, such asdivinylbenzene, divinyltoluene, divinylxylene and trivinylbenzene;

(5) Aliphatic or alicyclic unsaturated hydrocarbon: (5-1) olefin-basedmonomer (monoene), such as alkene [ethylene, propylene, butene-1,isobutylene, 3-methylbutene-1, pentene-1, heptene-1,4-methylpentene-1,diisobutylene, octene, dodecene, octadecene, 1-olefin(C20 to C36) etc.],and cycloalkene [cyclohexyene etc.]; (5-2) alkadiene, such as C4 to C12chain structure alkadiene (butadiene, isoprene, neoprene, 1,3- and1,4-pentadiene, 1,6-hexadiene, 1,3- and 1,7-octadiene, 1,3-dodecadieneetc.), and C5 to C12 cyclic alkadiene (cyclopentadiene,dicyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene etc.); and(5-3) terpene [pyrene, limonene etc.];

(6) Epoxy group (glycidyl group etc.)-containing monomer, such asglycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate,p-vinylphenylphenyloxide, 3,4-dihydro-1,2-pyran and (meth)allyl glycidylether;

(7) Nitrile group-containing monomer, such as AN, methacrylonitrile,cyanoST and cyanoalkyl(C2 to C4) (meth)acrylate [cyanoethyl(meth)acrylate etc.];

(8) Hydroxyl group and/or ether bond-containing monomer other than theaforementioned (1-2);

(8-1) Unsaturated mono- and polyol: C2 to C24 unsaturated monohydricalcohol, such as alkenol [vinyl alcohol, (meth)allyl alcohol,(iso)propenyl alcohol, crotonyl alcohol etc.], aromatic unsaturatedalcohol [cinnamyl alcohol, p-hydroxylstyrene etc.] and alkynol[propargyl alcohol etc.]; and unsaturated (poly)ether mono- and polyol,such as alkenyl or alkenylaryl (C2 to C24) ether of low-molecular polyolof the aforementioned (a22) or its AO adduct [vinyl ether, (meth)allylether, (iso)propenyl ether, crotonyl ether, cinnamyl ether, vinyl phenylether etc.], AO(C2 to C4) adduct of the aforementioned unsaturatedmonohydric alcohol];

(8-2) Unsaturated ether, such as hydrocarbyl(C1 to C20)ether ofunsaturated mono- and polyol [aforementioned (8-1)], such asmethoxyPEG(meth)allyl ether;

(9) Vinylester-based monomer:

Esters with unsaturated alcohol [aforementioned (8)] and carboxylic acid[C1 to C30 monocarboxylic acid described in aforementioned (1-2)], suchas vinyl ester (vinyl formate, vinyl acetate, vinyl propionate, vinylbutyrate, vinyl benzoate, vinylmethoxy acetate etc.), isopropenylacetate, (meth)allyl acetate, (meth)allyl benzoate, (meth)allyloxyethylacetate and acetoxystyrene; monoester of the aforementioned unsaturatedalcohol and polycarboxylic acid [aforementioned (h4)]; polyfunctionalvinyl ester, such as monoester of the aforementioned unsaturated alcoholand polycarboxylic acid [aforementioned (h4)]; polyfunctional vinylester, such as polyester(diester etc.) of the aforementioned unsaturatedalcohol and the aforementioned polycarboxylic acid, and ester of theaforementioned unsaturated alcohol and the aforementioned (2)unsaturated mono- or dicarboxylic acid [(meth)acrylate etc.];

(10) Halogen-containing vinyl-based monomer, such as halogenatedunsaturated hydrocarbon [vinyl chloride, vinyl fluoride, vinylidenechloride, vinylidene fluoride, (meth)allyl chloride, mono- anddi-chloroST chloroprene, fluorinated olefin described in U.S. Pat. No.5238767], and halogen-substituted alkyl (meth)acrylate [fluorinatedalkyl (meth)acrylate described in U.S. Pat. No. 5,238,767];

(11) Cationic group (amino group or quaternary ammonium saltgroup)-containing unsaturated monomer other than the aforementionedones: amino group (primary, secondary or tertiary)-containingunsaturated hydrocarbon, such as alkenylamine [mono- anddi-(meth)allylamine, crotylamine etc.] and amino group-containingstyrene-based monomer [aminoST, N,N-dimethylaminoST, vinylbenzylamineetc.], and heterocyclic amino group-containing unsaturated monomer[4-vinylpyridine, 2-vinylpyridine, 2-methyl-5-vinylpyridine,vinylimidazole, N-vinylpyrrole, N-vinylcarbazole etc.]; productsobtained by neutralizing or quaternarizing them [the same products asthose of aforementioned (1-3)]], such as vinylbenzyltrimethylammoniumsalt;

(12) Unsaturated ketone, such as vinyl methyl ketone, vinyl ethylketone, vinyl phenyl ketone, and polyfunctional unsaturated ketone(divinyl ketone etc.);

(13) Sulfur-containing unsaturated monomer, such as p-vinyldiphenylsulfide, vinylethyl sulfide, vinylethylsulfone, and polyfunctionalsulfur-containing unsaturated monomer (divinylsulfone, divinylsulfoxide, divinyl sulfide etc.); and

(14) Isocyanate group unsaturated monomer, such as isocyanatoethyl(meth)acrylate and m-isopropenyl-α,α-dimethylmethylbenzyl isocyanate.

Besides, monomers having at least one olefinic unsaturated groupdescribed in U.S. Pat. Nos. 4,130,523 and 3,424,706 can be also used.

Examples of the resin (V) include an acrylic-based resin (M), astyrene-based resin, a vinyl acetate-based resin, an olefin-based resin,an acrylonitrile-based resin, a halogen-containing vinyl-based resin,and a mixture of two or more of them.

Examples of the resin (M) include a (co)polymer of at least one(meth)acrylic acid ester (1) and a copolymer of at least one (4) and atleast one other monomer. Among (1), preferable is (1-1), andparticularly preferable is alkyl (meth)acrylate. Further preferable aremethyl methacrylate, 2-ethylhexyl methacrylate and butyl acrylate(hereinafter, abbreviated as MMA, EHMA and BA, respectively),particularly, joint use of them. Other monomer is selected from thegroup consisting of (2) to (14) and, among them, preferable are (4)(particularly, ST), (6) (particularly AN) and joint use of them. Acontent of (1) among (M) is usually 20 to 100%, preferably 50 to 99%based on a weight of total monomers (hereinafter, the same).

Examples of a styrene-based resin include a (co)polymer of at least onestyrene-based monomer (4) and a copolymer of at least one (4) and atleast one other monomer. Among (4), preferable is ST. Other monomer isselected from the group consisting of (1) to (3) and (5) to (14) and,among them, preferable are (1) [further preferably (1-1), particularlypreferably alkyl (meth)acrylate], (5) [further preferably (5-2),particularly preferably butadiene and cyclopentadiene], (6)(particularly, AN), and joint use of them. A content of (4) in astyrene-based resin is usually 20 to 100%, preferably 50 to 99%. Acontent of (1) is usually smaller than 20%.

Specific examples of a styrene-based resin include polyST, anST/α-methylST copolymer, and an ST/alkadiene-based resin (D). Examplesof the resin (D) include a (co)polymer of ST and at least one (5-2) anda copolymer of ST and at least one (5-2) and at least one other monomer.Other monomer is selected from the group consisting of (1) to (3),(5-1), (5-3) and (6) to (14) and, among them, preferable is (1) [furtherpreferably (1-1), particularly preferably alkyl (meth)acrylate], andparticularly preferable is (6) (particularly AN). Specific examples of(D) include a butadiene/ST copolymer, an AN/butadiene/ST copolymer (ABSresin), and a cyclopentadiene/ST copolymer. A ratio of ST/(5-2) inST/(D) is usually 20/80 to 80/20, preferably 30/70 to 70/30. A contentof other monomer is usually 40% or smaller, preferably 30% or smaller,and a content of (1) is smaller than 20%.

Examples of a vinyl acetate-based resin include a polymer of vinylacetate and a copolymer of vinyl acetate (usually 20 to 100%, preferably50 to 99%) and at least one other monomer [preferably (5) (particularly,ethylene), (8) (particularly, vinyl alcohol), other (9) (particularly,other vinyl ester) and joint use of two or more of them] [contents of(1) and (4) are smaller than 20%]. Specific examples include anethylene/vinyl acetate copolymer and its partial hydrolysate.

Examples of an olefin-based resin include a (co)polymer of at least oneolefinic-based monomer (5-1) (polyethylene, polypropylene, polybutene-1,polyisobutylene, poly-3-methylbutene-1, poly-4-methylpentene-1,polyethylene/propylene copolymer, propylene/isobutylene copolymer, C8 toC18 olefin copolymer etc.), and a copolymer of at least one (5-1)(usually 20 to 100%, preferably 50 to 99%) and at least one othermonomer [contents of (1), (4) and vinyl acetate are smaller than 20%].

Examples of an acrylonitrile-based resin include polyAN, and a copolymerof AN (usually 20 to 100%, preferably 50 to 99%) and at least one othermonomer (MMA, methyl acrylate, vinyl acetate, vinyl chloride, vinylidenechloride, N-methyl or ethylacrylamide, 2-methyl-5-vinylpyridine etc.)[contents of (1), (4), (5-1) and vinyl acetate are smaller than 20%].

Examples of a halogen-containing vinyl-based resin include a (co)polymerof at least one halogen-containing vinyl-based monomer (10) (polyvinylchloride, polyvinylidene chloride etc.), and a copolymer of at least one(10) (usually 20 to 100%, preferably 50 to 99%) and at least one othermonomer [contents of (1), (4), (5-1), vinyl acetate and AN are smallerthan 20%](e.g. vinylidene chloride copolymer described in U.S. Pat. No.3,424,706).

A ratio of a hydrophilic monomer [a monomer having a hydrophilic group(anionic group, cationic group, oxyethylene group, hydroxyl group etc.)among the aforementioned (1) to (14) and/or reactive emulsifierdescribed later] in the resin (V) is preferably 10% or smaller,particularly preferably 0.1 to 8%. A ratio of a polyfunctional monomeris preferably 5% or smaller, particularly preferably 1% or smaller.

Resin (V) has Mn of usually 2,000 to 2,000,000 or larger, preferably10,000 to 1,500,000.

A process for preparing (V) and its aqueous dispersion are notparticularly limited, but includes a process for preparing directly anaqueous dispersion of (V) by emulsification polymerization or suspensionpolymerization, and a process for preparing melt-like or solution-like(V) by bulk polymerization or solution polymerization. Preferable areemulsification polymerization and suspension polymerization methods. Anaqueous dispersion of (V) obtained as melt-like or solution-like statecan be prepared by emulsifier emulsification as in the aforementioned(U).

Upon polymerization, the known polymerization initiator, emulsifier,chain transfer agent and organic solvent may be used.

Examples of a polymerization initiator include a radical polymerizationinitiator, such as an azo compound (AIBN, AVN, azobisisovaleric acidetc.); peroxide such as organic peroxide (benzoyl peroxide, dicumylperoxide, t-butyl hydroperoxide, lauroyl peroxide, cumenehydroperoxideetc.) and inorganic peroxide [persulfate (potassium persulfate, sodiumpersulfate, ammonium persulfate etc.), perborate, persuccinic acidetc.], as well as joint use of two or more of them. An amount of apolymerization initiator to be used is usually 0.1 to 5% relative to atotal amount of monomers. Examples of an emulsifier used inemulsification polymerization include surfactants exemplified as theaforementioned emulsifier, and reactive emulsifiers copolymerizable inan emulsification polymerization step. Examples of the reactiveemulsifier include anionic (meth)acrylic acid ester [sulfate ester saltof mono(meth)acrylate of (poly)oxyalkylene(C2 to C4)ether (EO 1 to 30mole adduct) of bisphenols or bisphenols substituted with hydrocarbyl(C1to C24)(bisphenol A, styrenated and/or benzylated bisphenol A), sulfateester salt of mono(meth)acrylate of (poly)oxyalkylene (C2 to C4)ether(EO 1 to 30 mole adduct) of polycyclic polyhydric phenol such asformaldehyde-condensate of styrenated and/or benzylated phenol, as wellas polyoxyalkylene(C2 to C4, p=2 to 200)mono(meth)acrylate sulfate estersalt etc.], anionic (meth)acrylamide [(meth)acrylamidealkane(C1 toC24)sulfonate salt etc.], anionic (meth)allylester [alkyl(C8 toC24)(meth)allylsulfosuccinic acid ester salt etc.](these salts includealkali metal salt, ammonium salt, amine salt, quaternary ammonium salt,etc.), and reactive emulsifiers described in European PatentEP0718379B1, and International Application PCT/JP01/09863. An amount ofan emulsifier to be used is usually 0.1 to 8%, preferably 0.5 to 5%relative to a total amount of monomers.

Examples of a chain transfer agent include mercaptans such asalkylmercaptan (butylmercaptan, dodecylmercaptan etc.); α-methylstyrenedimer; halogenated hydrocarbon such as chloroform, carbon tetrachlorideand carbon tetrabromide; enol ethers such as those described in JP-ANo.55-31880; as well as a mixture of two or more of them. An amount of achain transfer agent to be used is usually 5% or smaller, preferably 0.1to 3% relative to a total amount of monomers.

Examples of an organic solvent include organic solvents exemplified forthe aforementioned (a214). Preferable are ketones (particularly, MIBK)and aromatic hydrocarbons. An organic solvent may be removed bydistillation after polymerization, etc.

A weight average particle diameter of an aqueous dispersion of (V)obtained in these methods is usually 0.005 to 4 μm, preferably 0.01 to 4μm, particularly preferably 0.01 to 3 μm. Dispersions (I) and (II) whena part of the resin (A) is (V) can be prepared by II-1) a method ofpreparing an aqueous dispersion of a vinyl-based resin (V1) in advanceas described above, according to the aforementioned (II), and thenintroducing and dispersing a melt or solution-like other resin (A2)[aresin other than an addition polymerization system resin, such as (U)and/or (E)] in an aqueous dispersion of (V1) using an emulsifyingmachine, in the state where the aqueous dispersion is flown or stirred;or conversely, (II-2) a method of preparing an aqueous dispersion ofother resin (A1) in advance as described above, and introducing anddispersing a melt or solution-like vinyl-based resin (V2) in an aqueousdispersion of (A1) using an emulsifying machine, in the state where theaqueous dispersion is flown or stirred.

In this case, aqueous dispersions (I) and (II) in which (V1) and (A2) or(V2) and (A2) have different particle diameters can be formed as in thecase of the aforementioned (U). For example, in order that (A2) has alarger particle diameter by the method of II-1), there are 1) a methodof weakening hydrophilicity of (A2), 2) a method of decreasing an amountof an emulsifier to be added, 3) a method of reducing a shear force atemulsification of (A2), and a combination of two or more of them. Apreferable amount of an emulsifier in the case of 2) is as described forthe case of the aforementioned (U).

In the aforementioned case, a dispersion of (V) constituting a part of(A) may comprise one kind of (V), or may comprise (V)s having two ormore different particle diameters. The latter dispersion can be preparedas in the case of the aforementioned (U).

Properties of Resins Constituting (P1) and (P2)

A difference in HLBs of resins constituting (P1) and (P2) in a particlediameter distribution curve of aqueous dispersions (I) and (II) of thepresent invention is 0.1 to 10, preferably 2 to 8, further preferably 3to 7. When a difference in HLBs is 0.1 or larger, since upon preparationof an aqueous dispersion of resins constituting (P2), resins can bedispersed using a small amount of a surfactant, water resistance of acoated film after drying tends to be improved, and adherability with asubstrate tends to be improved. If a difference in HLBs is 0.1 orlarger, even when a surfactant is not used, it is not necessary tochange a mechanical shear force greatly and, thus, a desired aqueousdispersion can be obtained. On the other hand, if a difference in HLBsis 10 or smaller, hydrophilicity of a resin having larger HLB does notbecomes too great, and it does not approach water-soluble, therefore, astable aqueous dispersion is easily obtained. Herein, HLB is HLB of anOda method, and is calculated by the following equation from organicproperty and inorganic property values of an organic compound [RyoheiOda, Teijin Times, 22, No.9 (1952)].HLB=10×inorganic property/organic property

In the present invention, a peaktop particle diameter of (P1) in aparticle diameter distribution curve measured by a photon correlationmethod is preferably 0.1 to 4 μm, further preferably 0.1 to 3.5 μm,particularly preferably 0.2 to 3 μm, especially preferably 0.3 to 2 μm.

In addition, a peaktop particle diameter of (P1) in a particle diameterdistribution curve measured by an ultrasound measuring method ispreferably 0.1 to 4 μm, further preferably 0.3 to 3 μm, particularlypreferably 0.4 to 2 μm.

When a peaktop particle diameter of (P1) is 4 μm or smaller, a particlesettles with difficulty over days, and storage stability is improved.

A ratio of a peaktop particle diameter of (P1) and a peaktop particlediameter of (P2) is preferably 2/1 to 100/1, further preferably 2.2/1 to20/1, particularly preferably 2.5/1 to 15/1 in a photon correlationmethod and in an ultrasonic measuring method. If this ratio is at least2/1, there is a tendency that a low viscosity is retained even at a highconcentration and, if this ratio is in a range not exceeding 100/1,there is a tendency that storage stability is improved.

In addition, a peaktop particle diameter of (P2) is preferably 0.01 to 1μm, further preferably 0.01 to 0.3 μm, particularly preferably 0.03 to0.2 μm, especially preferably 0.05 to 0.2 μm in a photon correlationmethod and in an ultrasonic measuring method.

If a peaktop particle diameter of (P2) is 0.01 μm or larger, there is atendency that a viscosity is lowered, and flowability is further better.

In addition, in both of a photon correlation method and an ultrasonicmeasuring method, there is at least one valley between (P1) and (P2) ina particle diameter distribution curve and, among valleys, a height of alowest valley (e.g. height of point v in FIG. 1, and point v in FIG. 2)is preferably 80% or smaller, further preferably 50% or smaller,particularly preferably 30% or smaller of a height of (P2). If a heightof this valley is 80% or smaller of a height of (P2), an aqueousdispersion having a sufficiently low viscosity is obtained.

In addition, it is preferable that at least one of resins forming (P1)and (P2) has a hydrophilic group (Q) having the number of groupsinherent to an atomic group of 0.3 or larger (further preferably 1.5 orlarger, particularly preferably 2 or larger) by a Davis method. Examplesof a hydrophilic group Q include an ionic group (anionic group, cationicgroup etc.) and a nonionic group exemplified for the aforementionedself-emulsifying (U). Preferable is an anionic group, and particularlypreferable are an alkyl metal salt (sodium salt etc.) of a carboxylgroup and an alkali metal salt (sodium salt etc.) of a sulfonic acidgroup.

When a resin is a resin having Q having the number of groups of 0.3 orlarger, particularly, upon preparation of an aqueous dispersion of aresin forming (P2), since the resin can be dispersed using a smallamount of a surfactant, there is a tendency that water resistance of acoated film after drying is improved, and adherability with a substrateis improved. In addition, even when a surfactant is not used, it is notnecessary to change a mechanical shear force greatly and, thus, adesired aqueous dispersion can be obtained.

It is preferably that a content of Q in a resin in resins forming (P1)and resins forming (P2) is preferably 0.02 to 30%, particularlypreferably 0.05 to 15% based on a weight of resins, and a difference incontents of Q in resins forming (P1) and (P2) is 0.1% or larger. When Qis an ionic group, a difference in contents of Q is further preferably0.03 to 10%, particularly preferably 0.5 to 3%. When Q is a nonionicgroup, a difference in contents of Q is further preferably 0.5 to 20%,particularly preferably 1 to 10%. A content of Q can be obtained bycalculating a total of Q charged in a step of preparing a resin,relative to a finished resin.

A ratio of resins constituting (P1) and (P2) is usually 10/90 to 95/5,preferably 50/50 to 90/10. A total of resins constituting (P1) and (P2)is preferably 30 to 100%, particularly preferably 50 to 100% based on atotal weight of all resins.

Examples of a dispersing medium used in an aqueous dispersion usuallyinclude water, and a hydrophilic organic solvent. Examples of ahydrophilic organic solvent include a hydrophilic organic solvent havingsolubility in water of 30 g or more/100 g water among organic solventsexemplified in the aforementioned (a214), for example, monohydricalcohol (methanol, ethanol, i-propanol etc.), glycols (EG, PG,diethylene glycol etc.), tri- or more-hydric alcohols (GL etc.), andcellosolves (methyl and ethylcellosolve, etc.). Among dispersing media,preferable is an aqueous medium, particularly water. When a hydrophilicorganic solvent is used jointly, usually, it is preferable that ahydrophilic organic solvent is 10% or smaller based on a total ofdispersing media.

The aqueous dispersion of the present invention can be used in utilitiessuch as paints, coating agents, adhesives, pressure -sensitive adhesivesand fiber and textile processing agents explained below.

Paints and Coating Agents

The aqueous dispersion of the present invention can be used as a bindercomponent in paints (coating agents), and is usually applied to aqueouspaints.

Preferable in this utility are (U), (E), (M) and (D).

Paints may contain a crosslinking agent in order to improve coated filmperformance. A crosslinking agent includes the following (x1) to (x4):

(x1) Water-soluble or water-dispersible amino resin, such as a melamineresin and a urea resin containing an (alkoxy)methylol group and/or animino group [preferably melamine resin containing methylol group and/orimino group];

(x2) Water-soluble or water-dispersible polyepoxide, such as bisphenol Atype gylcidyl ether, hydrogenated bisphenol A type glycidyl ether,glycidyl ether of polyol [aforementioned (a221)(EG, GL, TMB, sorbitoletc.), and AO(C2 to C3) adduct thereof (PEG etc.)], and polyepoxide towhich an emulsifying agent (aforementioned surfactant etc.) is added toimpart water dispersibility [preferable is glycidyl ether of polyhydricalcohol, particularly preferably sorbitol poly(di- to hexa)glycidylether and GL poly(di- and tri)glycidyl ether];

(x3) Water-soluble or water-dispersible polyisocyanate compound, such aspolyisocyanate having a hydrophilic group (such as polyoxyethylenechain) in a molecule [“Coronate 3062” and “Coronate 3725” (manufacturedby Nippon Polyurethane Industry Co., Ltd.)etc.], and blockedpolyisocyanate [aforementioned (a1)(isocyanurate-modified IPDI etc.)blocked with a blocking agent (phenols, active methylene compound,lactam, oxime, bisulfite, tertiary alcohol, aromatic secondary amine,imide and mercaptan described in U.S. Pat. No. 4,524,104; (e.g. phenol,MEK, ε-caprolactone etc.)];

(x4) Others, polyethyleneurea(diphenylmethane-bis-4,4′-N,N′-ethyleneurea etc.).

An amount of a crosslinking agent to be added is usually 0 to 30%,preferably 0.1 to 20% based on a solid matter weight of an aqueousdispersion.

If necessary, one or more other additives such as a pigment, a pigmentdispersant, a viscosity adjusting agent, an anti-foaming agent, aleveling agent, an antiseptic, a degradation-preventing agent, astabilizer and an anti-freezing agent may be added to paints.

Examples of a pigment include inorganic pigments such as white pigments(titanium white, zinc white, lithopone, white lead etc.), transparentwhite pigments (calcium carbonate, barium sulfate, calcium silicateetc.), black pigments (carbon black, animal black, red lead etc.), greypigments (zinc powder, slate powder etc.), red pigments (rouge, red leadetc.), brown pigments (amber, iron oxide powder, Vandyke brown etc.),yellow pigments (chrome yellow, zinc chromate, yellow iron oxide etc.),green pigments (chromium green, chromium oxide, viridian etc.), bluepigments (ultramarine, Prussian blue etc.), purple pigments (marspurple, pale cobalt purple etc.) and metallic pigments (aluminum flake,copper bronze flake, mica iron oxide, mica flake etc.); as well asorganic pigments such as natural organic pigments (Cotinil lake, Madalake etc.), and synthetic organic pigments such as nitroso pigments(Naphthol Green Y, Naphthol Green B etc.), nitro pigments (NaphtholYellow S, Pigment Chlorin, Litol Fast Yellow GG etc.), pigment dye typeazo pigments (Toluidine Red, Hansa yellow, Naphthol AS-G etc.), azo lakemade from water-soluble dyes (Persia Orange, Ponso 2R, Buildo B etc.),azo lake made from hardly soluble dyes (Risol Red, Born Malune, Red Lakeetc.), lake made from basic dyes (Fanal Color etc.), lake made fromacidic dyes (Acid Green Lake, Peacock Blue Lake etc.), xanthan lake(eosin etc.), anthraquinone lake (alizarin lake, purpurine lake etc.),pigments from vat dyes (indigo, argon yellow etc.), and phthalocyaninepigments (phthalocyanine blue, phthalocyanine green etc.).

Examples of a pigment dispersant include various surfactants [anionic,cationic, nonionic, amphoteric, polymer (Mn=1,000 to 20,000)]exemplified as an emulsifier in the aforementioned emulsifier-emulsifiedtype aqueous resin dispersion.

Examples of a viscosity adjusting agent include a thickener, such as aninorganic viscosity adjusting agent (sodium silicate and bentonite), acellulose viscosity agent (methylcellulose, carboxymethylcellulose,hydroxymethylcellulose etc., Mw is usually 20,000 or larger), aproteinaceous agent (casein, sodium caseinate, ammonium caseinate etc.),acrylic agent (sodium polyacrylate, ammonium polyacrylate etc., Mw isusually 20,000 or larger), and vinyl agent (polyvinyl alcohol etc., Mwis usually 20,000 or larger). Acrylic and vinyl viscosity adjustingagents are preferable.

Examples of an anti-foaming agent include long chain alcohols (octylalcohol etc.), sorbitan derivatives (sorbitan monoolate etc.), andsilicone oils (polymethylsiloxane, polyether-modified silicone,fluorine-modified silicone etc.); examples of an antiseptic includeorganic nitrogen sulfur compounds and organic sulfur halogen compoundantiseptics; examples of a degradation-preventing agent and a stabilizer(ultraviolet absorbing agent, antioxidant etc.) include hindered phenolseries, hindered amine series, hydrazine series, phosphorus series,benzophenone series, and benzotriazole series; examples of ananti-freezing agent include EG and PG.

An amount of these components to be incorporated is different dependingon utilities, and generally, in the case of pigment paint, an amount ofan aqueous resin dispersion is 10 to 300 parts (solid matters), anamount of a viscosity adjusting agent is 0 to 5 parts, an amount of ananti-foaming agent is 0 to 5 parts, an amount of an antiseptic agent is0 to 5 parts, an amount of a degradation-preventing agent or astabilizer is 0 to 5 parts, and an amount of an anti-freezing agent is 0to 5 parts relative to 100 parts of a pigment. In addition, in a clearpaint, usually, an amount of an anti-foaming agent is 0 to 3 parts, anamount of an antiseptic agent is 0 to 3 parts, an amount of anultraviolet-ray preventing agent is 0 to 3 parts, and an amount of ananti-freezing agent is 0 to 8 parts relative to 100 parts of an aqueousresin dispersion (solid matters).

A pigment aqueous paint can be prepared by mixing a pigment dispersantinto the aqueous resin dispersion of the present invention, adding apigment thereto to disperse it and, if necessary, adding other additive,and filtering undispersed materials. A dispersing machine (attrizer,bead mill, three-roll, ball mill etc.) can be used for dispersing theaforementioned materials.

A paint comprising the aqueous dispersion of the present invention canbe coated by the conventional coating means (spray coating, brushcoating, roll coating etc.). A viscosity of a paint is appropriatelyselected depending on a coating method. For example, in the case ofspray coating, preferably, a viscosity at a shear rate of 1000 s⁻¹ is 20to 50 mPa·s and a viscosity at a shear rate of 10 s⁻¹ is 180 to 280mPa·s. When a viscosity at a shear rate of 1000 s⁻¹ is 50 mPa·s orsmaller, a paint is easily ejected from spraying. When a viscosity at ashear rate of 10 s⁻¹ is 180 mPa·s or larger, sagging hardly occurs.These viscosities are measured with a high-shear-viscometer (“HSV-2”manufactured by Nippon Seiki Co., Ltd.).

A paint comprising the aqueous dispersion of the present invention canbe coated on a subject to be coated directly or via a primer, monolayercoating or multilayer (2 to 8 layers) recoating is possible, and thepaint can be used in any of undercoating, intercoating and topcoating.Examples of a subject to be coated include timbers, papers, leathers,metals (aluminum, iron, copper, various alloys etc.), plastics (vinylchloride-based resin, acrylic-based resin, styrene-based resin etc.),and inorganic materials (concrete, slate, calcium silicate plate etc.).Examples of a form of a subject to be coated include films, fibers,nonwoven fabrics, sheets, plates, bars, pipes, blocks, various moldedarticles, and structures.

A paint comprising the aqueous dispersion of the present invention isuseful in various paints and coating agents (topcoating, intercoatingand undercoating paints for automobiles, construction paints,rust-preventing coating for metals, flaw-preventing coating for metalsand resins, water resistant coating for papers and leathers, solventresistant coating and moistureproof coating, as well as polishingcoating floors), and various binders (automobile coating binders, outerwall coating binders, coated paper binders, and ceramic binders). Anamount of a paint to be coated is different depending on utility andpurpose, and an amount as an aqueous paint itself (wet-state) is usually0.5 to 1,000 g/m², preferably 1 to 300 g/m².

Drying condition after coating is from a normal temperature to around200° C. A drying format is not particularly limited, but for example,hot air, infrared-ray, and electric heater are used.

Adhesive

The aqueous dispersion of the present invention is used as a main agentin an adhesive.

Preferable in this utility are (U), (E), (M) and an epoxy resin.

In order to further manifest adhering function, a crosslinking agent canbe added to an adhesive, if necessary, other additives such as apigment, a pigment dispersant, a viscosity adjusting agent, astabilizer, an antiseptic and an anti-freezing agent can be added to anadhesive. These crosslinking agent and additive include the same agentsas those exemplified for the aforementioned paint.

A solid matter ratio of the aqueous dispersion and the crosslinkingagent is 50 to 99:1 to 50, preferably 70 to 97:3 to 30. When a ratio ofa crosslinking agent is 1 or larger, a sufficient adhering strength anddurability are obtained and, when the ratio is 50 or smaller, an adheredarticle scarcely becomes fragile, being preferable. A method of mixingthe aqueous dispersion and the crosslinking agent is not particularlylimited, but examples include mixing by conventional stirring andmethods using a mixing apparatus (paint conditioner, ball mill, kneader,sand grinder, flat stone mill etc.).

Examples of means for applying an adhesive to an adherend include brushcoating, roll coating, spray coating, curtain flow coating and dipping.Adhesion can be performed by applying an adhesive to a adherend, andlaminating this as it is (without drying) with other adherend (wetadhesion), or after drying, laminating with other adherend (dryadhesion), and curing an adhesive layer. Alternatively, adhesion may beperformed by curing by intervening a dried film of an adhesive betweenadherends. Curing can be performed by aging at a normal temperature orunder heating (e.g. around 60 to 80° C.), or by, after aging at a normaltemperature, heating to around 60 to 80° C. to promote curing.

An adherend is not particularly limited, but an adhesive can be widelyused in substrates such as timbers, resin films, rubbers, leathers,papers and metals.

An adhesive comprising the aqueous dispersion of the present inventionis useful in, for example, woodworking adhesives, metal parts adhesives,plastic adhesives, electronic substrate adhesives and cloth adhesives.

Fiber and Textile Processing and Treating Agent

The aqueous dispersion of the present invention can be widely used infiber and textile processing binders (pigment printing binders, nonwovenfabric binders, reinforcing fiber sizing agents, antibacterial bindersetc.) or coatings (waterproofing coating, water repellant coating,anti-stain coating etc.), and artificial leather-synthetic leather rowmaterials.

Preferable for pigment printing binders are (U), (E) and (M); preferablefor nonwoven binders are (U), (E) and (M); preferable for reinforcingfiber sizing agents are (U), (E), (M) and an epoxy resin: preferable forantibacterial binders are (U), (E) and (M); preferable for coatings are(U), (E) and (M); preferable for artificial leather -synthetic leatherraw materials is (U).

When used as a pigment printing binder, if necessary, one or more of anemulsifier, a stabilizer (ultraviolet absorbing agent, antioxidantetc.), a thickener, a film forming aid and other aid may be added to theaqueous dispersion. Examples of an emulsifier include the sameemulsifiers as those described above. In particular, an anionicsurfactant and a nonionic surfactant are preferable. Examples of astabilizer and a thickener include the same stabilizers and thickenersas those exemplified in the aforementioned paints. Examples of a filmforming aid include N-methyl-2-pyrrolidone; examples of other aidinclude printing suitability imparting agent and gum up preventingagent.

Pigment printing can be performed by printing onto fabrics as inconventional pigment printing. Specifically, for example, a color paste(in which a pigment is finely and uniformly dispersed in water), theaqueous dispersion of the present invention, a thickener, and other aidsare incorporated to prepare a printing paste, and this is printed onfabrics. A paddle-mixing tank etc. is used for incorporation. Anautoscreen printer, a rotary screen printer, and a roller printer can beused in printing. Natural fibers (cotton, flax, wool silk etc.),semi-synthetic fibers (rayon, acetate etc.), and synthetic fibers(polyester, polyamide, polyAN, polyolefin etc.) can be used in fabrics.

Examples of a reinforcing fiber to be applied when used as reinforcingfiber sizing agents include inorganic fibers (glass fiber, carbon fiberetc.) and high strength organic fibers (polyamide fiber, polyester fiberetc.) described in British Patent No.1543099.

When used as glass fiber sizing agents, if necessary, one or moreadditives such as a silane coupling agent (y-aminopropylethoxysilane,y-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane,vinyltriethoxysilane, y-glycidoxypropyltrimethoxysilane etc.), alubricant (fatty acid amide, soap etc.), an antistatic agent (theaforementioned surfactant etc.), a plasticizer (phthalic acid ester,adipic acid ester etc.), and an anti-foaming agent (as described above)may be added to the aqueous dispersion of the present invention.

Sizing agents may be used with other sizing agents, and examples includestarch, processed starch, dextrin, amylose, gelatin,carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone,polyvinyl acetate, aqueous polyester resin, aqueous epoxy resin, andaqueous acrylic resin. The aqueous dispersion and an arbitrary additiveare incorporated to prepare a treating solution, this is applied tofibers and, if necessary, heated and dried to fix this. A mixing tank(paddle type) etc. is used for incorporation. The concentration of atreating solution is usually 1 to 10%. Application to fibers isperformed by roller coating, spray coating, immersion coating etc. Anamount to be adhered to fibers is usually 0.1 to 10%. Drying and fixingcan be performed, for example, at 50 to 100° C.

When used as antibacterial binders, coatings, or artificial leathersynthetic leather raw materials, additives, the concentration of atreating solution, means for application to fibers, an amount to beadhered to fibers, and treating conditions etc. may be the same as thosedescribed above, and can be appropriately adopted depending onutilities.

BEST MODE FOR CARRYING OUT THE INVENTION

The following Examples illustrate the present invention morespecifically, but the present invention is not limited by them.

In the following Examples, a dispersing machine I used is arotator-stator emulsifying machine (manufactured by M Technique, ClearMix LCM-0.8S), and a dispersing machine II is a rotator-statordispersing machine [manufactured by Ebara Corporation, Ebara MilderMDN303V-D]. Unless otherwise indicated, a viscosity was measured at 25°C. and a rotation rate of 60 rpm using a rotary viscometer (manufacturedby TOKIMEC(K.K.)). Stability with day was assessed as follows: 80m1 of adispersion (or aqueous paint) was taken in a glass settling tube havingan inner diameter of 2.5 cm and a volume of 100 ml, and stored at 25° C.Appearance was checked once per day, and stability was assessed by daysuntil a separation interface appeared. In the case where separation doesnot occur after passage of 90 days, this is described as >90.

PREPARATION EXAMPLES 1 TO 7 Preparation of Up

According to formulation (parts) described in Table 1, initial chargingcomponents were charged into an autoclave equipped with a thermometer, astirrer and a nitrogen blowing tube, the atmosphere was replaced withnitrogen, and thereafter, urethanation was performed at 80° C. whilestirring, then this was cooled to 40° C., additional acetone and TEAwere added, and uniformly mixed to obtain a solution of Up (Up1 to Up7).A NCO content (%) of Up (solid matter) contained in those solutions isshown in Table 1. All of PMPA, PTMG and PHCD used had Mn of 2,000, andPCLD was PLACCEL L220AL manufactured by Daisel Chemical Industries Co.,Ltd.

PREPARATION EXAMPLES 8 TO 14 Preparation of Dispersion of (U)

Using each Up described in Table 2, a dispersion of (U) was prepared bythe following method I or method II.

Method I:

Using a dispersing machine I, Up and water were continuously suppliedinto a rotator-stator rotating at a rotation number of 7,000 to 9,000rpm, at a rate of 45 parts/min and at a retention time of 2 minutes, toperform dispersing, and Up dispersed in water was stored in a receivingtank equipped with a stirrer. Then, in the receiving tank, Up dispersedin water was subjected to a chain extension reaction under the following1's or 2's condition, until a NCO group was substantially consumed, andacetone was distilled off under reduced pressure. Thereafter, the sameamount as that of water distilled off with acetone, of water, and thesame amount as that of TEA distilled off with acetone, of TEA wereadded, respectively, to obtain a dispersion of (U)(U1 to U7).

Condition 1: Such an amount that an equivalent ratio of NCO/amino groupwas 1/1, of EDA was added, and a chain was extended while stirring at30° C. for 30 minutes.

Condition 2: As such (without addition of EDA) was stirred at 50° C. for12 hours, and a chain was extended with water.

Method II:

In advance, 125 Parts of water was charged into a four-neck flaskequipped with a thermometer, a stirrer and a condensing tube, 230 partsof Up was placed under high speed stirring, and dispersing wasperformed. To the resulting dispersion was further added 4 parts of asolution in which 2 parts of EDA had been dissolved in 2 parts of water,the materials were stirred at 40° C. for 12 hours, to perform a chainextension reaction, acetone was distilled off under reduced pressure,the same amounts as those of water and TEA distilled off with acetone ofwater and TEA were added, respectively, to obtain a dispersion of (U).

TABLE 1 Preparation Example No. 1 2 3 4 5 6 7 Initial chargingcomponents PMPA 73 73 — — — — — PTMG — — 73 73 — — — PHCD — — — — 73 73— PCLD — — — — — — 99 BD 3 3 5 5 — — — DMPA 5 2 5 2 5 2 2.8 Acetone 5 55 5 5 5 54 IPDI 34 33 33 33 25 25 24 Additional 36 36 36 36 36 36 50acetone TEA 4 2 4 2 4 2 2 Up symbol Up1 Up2 Up3 Up4 Up5 Up6 Up7 NCOcontent 7.7 7.9 7.8 8.0 6.3 6.6 3.9

PREPARATION EXAMPLE 15 Preparation of Dispersion of (E)

4 Parts of toluene, 2 parts of MIBK, 11 parts of BEPD, 8 parts of HD, 1part of PE, 14 parts of sebacic acid and 14 parts of isophthalic acidwere charged into a four-neck flask equipped with a thermometer, astirrer, a water separating tube, and a gas blowing tube, the materialswere dehydrated at 180° C. under stirring while introducing a nitrogengas, and esterification was performed until an acid value became 11.4.Then, the resulting solution of (E) was introduced into a four-neckflask containing 1 part of TEA, 1 part ofpolyoxyethylene(p=40)laurylether and 80 parts of water while high speedstirring, and toluene and MIBK were distilled off under reduced pressureto obtain a dispersion (E1) of (E).

PREPARATION EXAMPLE 16 Preparation of Dispersion of (M)

15 Parts of MMA, 32 parts of EHMA, 30 parts of BA, 5 parts of AN, 10parts of ST, 8 parts of a polymerizable emulsifier and 100 parts ofwater were mixed to prepare a monomer dispersion. Then, 35 parts ofwater, 8 parts of a polymerizable emulsifier, 5 parts of ammoniumpersulfate, and 0.4 part of diammonium hydrogen phosphate were chargedinto an autoclave equipped with a thermometer, a stirrer, a pressuregauge, a monomer solution introducing inlet, an initiator solutionintroducing inlet and a nitrogen blowing tube, the interior of acontainer was replaced with nitrogen, the aforementioned monomerdispersion was added dropwise at 75 to 85° C. over 6 hours whilestirring, and then stirring was continued at the same temperature for 3hours, thereafter 1 part of t-butylperoxy-2-ethyl hexanoate was added,and stirring was continued at the same temperature for 2 hours to obtaina dispersion (M1). A polymerizable emulsifier used was a sulfate estersalt of mono(meth)acrylate of polyoxyethylene ether of a styrenatedphenol formaldehyde condensate [manufactured by Nippon Emulsifier(K.K.), Antox MS-60].

HLB and a hydrophilic group content (%) of resins constituting thedispersions obtained in Preparation Examples 8 to 16, as well as aconcentration (%) and a viscosity (mPa·s) of the dispersions are shownin Table 2.

TABLE 2 Hydrophilic Preparation group Example Up Method ConditionDispersion HLB content Concentration Viscosity 8 Up1 I 1 U1 10.1 1.5 3520 9 Up2 I 2 U2 9.7 0.8 35 15 10 Up3 I 1 U3 11.4 1.6 35 15 11 Up4 I 2 U410.0 0.7 35 20 12 Up5 I 1 U5 11.1 1.5 35 16 13 Up6 I 2 U6 9.8 0.8 35 1814 Up7 II — U7 9.6 0.8 35 13 15 — — — E1 7.1 3.8 45 30 16 — — — M1 9.08.4 45 85

EXAMPLES 1 TO 5 AND COMPARATIVE EXAMPLE 1 TO 3

Two kinds of dispersions having a proportion of solid matters to beincorporated described in Table 3, were blended, stirred for 30 minutes,or one kind of the dispersion was concentrated by an evaporator at 60°C., whereby, dispersions having a solid matter concentration of 65% wereobtained.

TABLE 3 Comparative Examples Examples 1 2 3 4 5 1 2 3 Dispersion SymbolU1 U3 U5 U1 U2 U1 U2 U1 Part 25 30 20 25 75 100 100 25 Dispersion SymbolU2 U4 U6 E1 M1 — — U7 Part 75 70 80 75 25 — — 75

EXAMPLES 6 TO 8

The dispersion and Up were continuously and simultaneously supplied intoa dispersing machine II rotating at a rotation number of 9,000 rpm, for2 minutes at a supplying rate in the following Table 4, and thematerials were dispersed to obtain 1,860 parts of a dispersion. Thisdispersion was charged into a four-neck flask equipped with athermometer, a stirrer, and a condensing tube, an amount described inthe following Table 4 of a 10% aqueous EDA solution was added, themixture was stirred at 30° C. for 1 hour to subject Up to an extensionreaction, and acetone was distilled off under reduced pressure to obtaina dispersion having a solid matter concentration of 65%.

TABLE 4 10% aqueous Dispersion Up EDA Supply rate Supply rate solutionSymbol (parts/min) Symbol (parts/min) (parts) Example 6 U1 380 Up2 550100 Example 7 E1 380 Up1 80 23 Example 8 M1 170 Up2 550 100

EXAMPLE 9

A 10 φ×125 mm SPG membrane having a fine pore diameter of 0.05 μm(Shirasu porous glass membrane: manufactured by SPG Techno) was attachedto a membrane dispersion module (Ise Chemical Industries Co., Ltd.), aflow rate was adjusted so that U2 passed through the interior of the SPGmembrane at 20 parts/min, 40 parts of Up1 was supplied at a rate of 4.6parts/min from the outside of the SPG membrane, utilizing a backpressure (0.8 MPa) from the outside of a cylinder, passed through porouspores of the SPG membrane, and contacted with U2 in the interior, todisperse Up1. Thereafter, the dispersion was stirred at 50° C. for 12hours in a four-neck flask equipped with a thermometer, a stirrer, and acondensing tube, isocyanate at a molecular end was subjected to anextension reaction with water, and acetone was distilled off underreduced pressure to obtain a dispersion having a solid matterconcentration of 65%.

EXAMPLE 10

Water and Up1 were continuously supplied for 10 minutes into adispersing machine II rotating at a rotation number of 12,000 rpm, at arate of 146 parts/min and 184 parts/min, respectively, to prepare adispersion; subsequently, the aforementioned dispersion and Up2 werecontinuously supplied for 10 minutes into another dispersing machine IIrotating at a rotation number of 9,000 rpm, at a rate of 330 parts/minand 550 parts/min, respectively. Then, 8,800 parts of the resultingdispersion was charged into a four-neck flask equipped with athermometer, a stirrer and a condensing tube, 1,000 parts of a 10%aqueous EDA solution was added, the mixture was stirred at 30° C. for 1hour to perform a chain extension reaction, and acetone was distilledoff under reduced pressure to obtain a dispersion having a solid matterconcentration of 65%.

COMPARATIVE EXAMPLE 4

Up1 and water were continuously and simultaneously supplied for 2minutes into a dispersing machine II rotating at a rotation number of9,000 rpm, at a rate of 550 parts/min and 500 parts/min, respectively,to disperse the material to obtain 1,050 parts of a dispersion (A) ofUp1. 525 parts of A was further supplied for 1 minute into the samedispersing machine at a rotation number of 12,000 rpm, at a rate of 500parts/min, to disperse the material to obtain a dispersion (B) in whichUp1 was finely dispersed.

A and B were blended at a solid matter ratio of 75/25, in a four-neckflask equipped with a thermometer, stirrer and a condensing tube, 100parts of a 10% aqueous EDA solution was added, the mixture was stirredat 30° C. for 1 hour to subject Up1 to an extension reaction, and then,acetone was distilled off under reduced pressure to obtain a dispersionhaving a solid matter concentration of 65%.

COMPARATIVE EXAMPLE 5

According to the same manner as that of Comparative Example 4 exceptthat Up2 was used in place of Up1, a dispersion having a solid matterconcentration of 65% was obtained.

A particle diameter distribution of these dispersions were measured by aphoton correlation method (measuring method 1) or an ultrasonic method(measuring method 2), and an average particle diameter, a variationcoefficient, a skewness and a kurtosis of each of (P1) and (P2), a ratioof peaktop particle diameters of (P1)/(P2) and a ratio of heights ofpeaktops, as well as a ratio of a height of valley/(P2) were calculated.Those results are shown in Table 5. In addition, regarding thesedispersions, a coefficient A, a constant item B and a contribution rateof a relationship equation (1) between a concentration and a viscositywere obtained, a viscosity was measured, and stability with day wasassessed. Those results are shown in Table 6.

In addition, regarding these dispersions, a coefficient A, a constantitem B and a contribution rate of a relationship equation (1) between aconcentration and a viscosity were obtained, a viscosity was measured,and stability with day was assessed. Those results are shown in Table 6.

TABLE 5 Particle diameter Particle diameter distribution of (P1)distribution of (P2) (P1)/(P2) Average Average Particle Valley Measuringparticle Variation Skew- Kur- particle Variation Skew- Kur- Number ofdiameter Height height/ method diameter coefficient ness tosis diametercoefficient ness tosis peaks ratio ratio (P2) Examples 1 1 0.63 50 1.24.3 0.06 47 1.2 4.3 2  11/1 3.2/1  0/100 2 1 0.80 75 0.3 1.7 0.06 47 1.24.3 2  13/1 3.0/1  0/100 3 1 0.63 50 1.2 4.3 0.15 17 0.3 2.2 2   4/12.9/1  0/100 4 1 0.75 19 0.3 2.3 0.07 38 0.6 2.7 2  11/1 3.3/1  0/100 51 0.63 22 0.4 2.3 0.22 38 0.4 2.3 2   3/1 1.9/1  5/100 6 1 0.72 52 1.33.8 0.06 45 0.8 4.1 2  12/1 3.2/1  0/100 2 0.70 65 1.3 4.8 0.08 45 0.94.3 2   9/1 3.0/1  0/100 7 1 0.79 86 1.3 3.6 0.07 38 0.6 3.6 2  11/13.0/1  0/100 2 0.81 75 1.2 3.9 0.06 42 0.7 3.2 2  14/1 3.0/1  0/100 8 10.67 48 1.6 2.3 0.17 28 0.7 2.3 2   4/1 2.8/1 10/100 2 0.63 47 1.6 2.40.15 18 0.9 2.3 2   4/1 2.6/1 10/100 9 1 0.72 35 0.8 1.9 0.06 51 1.3 2.02  12/1 3.3/1  0/100 2 0.75 28 0.8 1.9 0.06 51 1.3 2.0 2  13/1 3.3/1 0/100 10 1 0.70 51 1.3 3.9 0.07 46 1.1 4.0 2  10/1 3.2/1  0/100 2 0.6962 1.2 3.8 0.07 48 1.2 3.7 2  10/1 3.2/1  0/100 Comparative Examples 1 10.08 53 1.3 4.3 — — — — 1 — — — 2 1 0.65 58 1.3 4.5 — — — — 1 — — — 3 14.70 160 −0.3 0.8 0.07 47 1.2 4.3 2  78/1 2.5/1  0/100 4 1 0.12 76 1.31.3 0.08 63 1.2 1.4 2 1.5/1 — 53/100 2 0.12 80 1.3 1.5 0.08 63 1.4 1.4 21.5/1 — 53/100 5 1 0.98 145 1.6 1.1 0.68 103 1.9 1.3 2 1.4/1 — 62/100 20.95 140 1.6 1.5 0.71 110 1.7 2.3 2 1.3/1 — 65/100

TABLE 6 Contri- Coefficient Constant bution Viscosity Stability A item Brate (mPa · s) with day Example 1 −0.015 1.16 0.89 3250 >90 Example 2−0.020 1.56 0.74 2350 >90 Example 3 −0.019 1.49 0.91 2600 >90 Example 4−0.020 1.56 0.74 3650 >90 Example 5 −0.019 1.49 0.99 1050 >90 Example 6−0.018 1.45 0.92 3050 >90 Example 7 −0.021 1.69 0.89 2200 >90 Example 8−0.020 1.48 0.92 2320 >90 Example 9 −0.021 1.65 0.89 3380 >90 Example 10−0.016 1.17 0.88 3020 >90 Comparative −0.007 0.67 0.96 >50000 >90Example 1 Comparative −0.008 0.74 0.94 35000 60 Example 2 Comparative−0.310 23.0 0.99 900 3 Example 3 Comparative −0.006 0.63 0.96 14200 60Example 4 Comparative −0.010 0.83 0.91 8800 60 Example 5

EXAMPLES 11 TO 20

Using respective dispersions obtained in Examples 1 to 10 andComparative Examples 1 to 5, aqueous paints were prepared as follows:

300 Parts of a dispersion was taken into a beaker, 165 parts ofion-exchanged water, and 0.1 part of a pigment dispersant [manufacturedby Sanyo Chemical Industries, Ltd., CARRYBON L-400] were added, and thematerials were stirred and mixed for 15 minutes at a rotation number of300 rpm using a propeller stirring wing. Then, this mixed solution wastransferred to a bead mill container, 60 parts of a pigment[manufactured by Sanyo Color Works Ltd., Emacol NS WHITE A 426], 0.1part of an anti-foaming agent [manufactured by San Nopco, Ltd.,Nopco8034L] and 75 parts of a crosslinking agent [manufactured by MitsuiCyanamide, Cymel 325] were added, 250 parts of zirconium beads having adiameter of 1 mm were added, the mixture was shaken for 2 hours, andbeads were removed to obtain an aqueous paint having a solid matterconcentration of 55%. A viscosity at SR1000s⁻¹ and 10s⁻¹ was measuredusing a high shear viscometer (manufactured by Nippon Seiki Co., Ltd.,HSV-2).

Since aqueous paints having a solid matter concentration of 55% obtainedfrom respective dispersions of Comparative Examples 1 to 5 have aviscosity at SR1000s⁻¹ of 45 to 60 mPa·s, and have a too high viscosityfor spray coating, those aqueous paints were diluted with ion-exchangedwater to obtain aqueous paints having a solid matter concentration of40%.

In addition, regarding aqueous paints having a solid matterconcentration of 55% obtained from dispersions of Comparative Examples 4and 5, in order to adjust a viscosity at SR1000s⁻¹ and SR10s⁻¹ to anoptimal viscosity, it was necessary to dilute aqueous paints withion-exchanged water and add 4.0 parts of a viscosity adjusting agent[manufactured by San Nopco, Ltd., SN Thickener A-636], and aqueouspaints having a solid matter concentration of 20% were finally obtained.

These aqueous paints were spray-coated on a 8 cm×15 cm aluminum platehaving a thickness of 1.0 mm, at a back pressure of 2.0 Kg/cm² using aspraying gun. Coating was performed at a thickness of 200 μm(wet-state), and the plate was dried at 80° C. using an air drier. Afterinitiation of drying, a weight was measured every one minute, and a timeuntil a change rate in a coated film weight after drying became 0.1% orsmaller (drying time) was measured. Thereafter, the plate was cooled toroom temperature, and a dry film thickness was measured with a contactdigital film thickness meter (manufactured by OZAKI MGG, GS-10). Inaddition, stability with day of these aqueous paints were assessed.

These results are shown in Table 7.

TABLE 7 Solid matter Drying Dry film Dispersion concentration Viscosity(mPa · s) time thickness Stability example No. (%) SR1000_(S) ⁻1SR10_(S) ⁻1 (min) (μm) with day Examples 11 Example 1 55 30 215 2110 >90 12 Example 2 55 33 235 2 112 >90 13 Example 3 55 30 220 2105 >90 14 Example 4 55 32 220 2 110 >90 15 Example 5 55 29 215 2113 >90 16 Example 6 55 28 230 2 106 >90 17 Example 7 55 32 230 2110 >90 18 Example 8 55 29 210 2 113 >90 19 Example 9 55 29 240 2115 >90 20 Example 10 55 32 220 2 113 >90 Comparative Examples 6Comparative 40 28 115 4 86 30 Example 1 7 Comparative 40 30 105 4 88 35Example 2 8 Comparative 40 23 110 4 83 32 Example 3 9 Comparative 40 21100 4 84 30 Example 4 10 Comparative 40 20 97 4 82 30 Example 5 11Comparative 20 31 235 7 46 19 Example 4 12 Comparative 20 33 220 7 43 18Example 5

INDUSTRIAL FIELD OF APPLICABILITY

The dispersion of the present invention exhibits a low viscosity even ata high concentration exceeding 65%, and has better stability with day.In addition, paints, adhesives, pressure-sensitive adhesives and fiberand textile processing and treating agents using the dispersion of thepresent invention are excellent in storage stability even at a highconcentration.

Since the paint of the present invention is also excellent in coatingstability, and has a high concentration, a drying rate can be improvedconsiderably, and it becomes possible to perform coating at a largethickness, thus, the paint contributes to great improvement inproductivity. An aqueous paint has a viscosity at high shear and lowshear, equivalent to a viscosity of the previous aqueous paint having asolid matter concentration level of 20% in which a viscosity adjustingagent is added, even at a high solid matter concentration of 55%, adrying rate can be improved considerably and, at the same time, itbecomes possible to perform coating at a large thickness, whilemaintaining the same level of coating stability as that of the perviousaqueous paint.

In addition, since the adhesive of the present invention has a lowviscosity even at a high concentration, immersion into an adhesionsubstrate is rapid, and a quick-drying adhesive is obtained. Inaddition, since an adhesive for dry laminating shortens a drying time,productivity of a laminating step can be improved.

Further, since a pigment printing binder has a high concentration, lackof thickness hardly occurs.

1. An aqueous dispersion comprising particles of at least one resinselected from the group consisting of a polyaddition resin, apolycondensation resin, an addition condensation resin, aring-opening-polymerization resin and an addition polymerization resin;wherein the particles exhibit at least two peaks in a particle diameterdistribution curve; at least one peak of the peaks comprises at leastone resin selected from the group consisting of a polyaddition resin, apolycondensation resin, an addition condensation resin and aring-opening-polymerization resin; the aqueous dispersion satisfies oneor both of the following (i) and (ii): (i) wherein in a particlediameter distribution curve for the aqueous dispersion, a highest peak(P1) and a second highest peak (P2) exhibit the particle distributioncurved exhibits the following properties: a ratio of a particle diametercorresponding to a maxima of (P1) to a particle diameter correspondingto a maxima of (P2) is in a range of 2/1 to 100/1; a ratio of a particlecount value at a maximum height of (P1) to a particle count value at amaximum height of (P2) is in a range of 1/1 to 10/1, (P1) and (P2) havea peak variation coefficient of a peak of 0.1 to 150%, (P1) and (P2)have a skewness of −10 to 10 and (P1) and (P2) have a kurtosis of 0 to10, and (ii) if a concentration range of an aqueous dispersion is 20 to70% by weight, the aqueous dispersion satisfies the following relationequation (1) having a coefficient A of −2 to 0 and a constant item B of1 to 5:1/log(η/−ηo)=Aφ+B  (1) wherein η0 and η represent a Brookfield viscosity(mPa·s, 25° C.) of water and the aqueous dispersion having a resinconcentration of φ% by weight.
 2. The dispersion according to claim 1,wherein the difference between a hydrophilic-lipophylic balance (“HLB”)of a resin represented by (P1) and an HLB of a resin represented by(P2), the difference in HLBs of the two resins being between 0.1 to 10.3. The dispersion according to claim 1, wherein (P1) has a peaktopparticle diameter of 0.1 to 4 μm.
 4. The dispersion according to claim1, wherein (P1) and (P2) have a ratio of a peaktop particle diameter of(P1)/ a peaktop diameter of (P2) in a range of 2.2/1 to 20/1.
 5. Thedispersion according to claim 1, wherein the particle diameterdistribution curve has a lowest valley not exceeding 80% of the heightof the peaktop of (P2) between (P1) and (P2).
 6. The dispersionaccording to claim 1, wherein the resin forming (P1) or (P2) is at leastone resin selected from the group consisting of a polyurethane resin, apolyester resin, a polyamide resin, a silicone resin, a polycarbonateresin, a phenol resin, an amino resin, an epoxy resin, an acrylic resinand a styrene resin.
 7. The dispersion according to claim 1, wherein atleast one of (P1) and (P2) contains a hydrophilic group (Q) having thenumber of groups inherent to an atomic entity by a Davis method of 0.3or larger.
 8. The dispersion according to claim 7, wherein thehydrophilic group (Q) is one or more selected from the group consistingof a carboxyl group, a carboxylate group, a sulfonic acid group, asulfonate group and an oxyethylene group.
 9. The dispersion according toclaim 7, wherein the resin forming (P1) and the resin forming (P2) havea difference in content of the hydrophilic group (Q) of 0.1% by weightof larger.
 10. The dispersion according to claim 1, wherein theconcentration of resin particles in the dispersion is 50 to 75% byweight.
 11. The dispersion according to claim 1, which comprises anaqueous dispersion of a resin comprising a resin (A1) and other resin(A2) each of (A1) and (A2) having two or more different particlediameters, and is obtained by dispersing a solution or a melt of (A2) ora precursor of (A2) in an aqueous dispersion of (A1) and, in the case ofa precursor, converting the precursor into (A2).
 12. The dispersionaccording to claim 11, wherein the precursor is dispersed into anaqueous dispersion of (A1) using at least one emulsifying machineselected from a rotator-stator emulsifying machine, a line millemulsifying machine, a static tube mixing emulsifying machine, avibration emulsifying machine, an ultrasonic shock emulsifying machine,a high pressure impact emulsifying machine, a membrane emulsificationemulsifying machine, a centrifugation thin membrane contact emulsifyingmachine and an anchor agitator emulsifying machine.
 13. The dispersionaccording to claim 11, wherein the aqueous dispersion comprises amixture of resin (A1) and resin (A2), wherein the mixture comprises 10to 50% by weight of (A1) and 50 to 90% by weight of (A2).
 14. Thedispersion according to claim 11, wherein the resin (A1) is apolyurethane resin obtained by adding polyamine to an aqueous dispersionof a urethane prepolymer having NCO terminal groups, and subjecting theprepolymer to chain extension.
 15. The dispersion according to claim 14,wherein the aqueous dispersion of a prepolymer is formed using anemulsifying machine selected from a rotator-stator emulsifying machine,a line mill emulsifying machine, a static tube mixing emulsifyingmachine, a vibration emulsifying machine, an ultrasonic shockemulsifying machine, a high pressure impact emulsifying machine, amembrane emulsification emulsifying machine, a centrifugation thinmembrane contact emulsifying machine and an anchor agitator emulsifyingmachine.
 16. The dispersion according to claim 14, wherein a chainextension reaction of the polyamine and the prepolymer is performed in abatch reaction apparatus.
 17. A powdery resin obtained from thedispersion as defined in claim
 1. 18. A paint, an adhesive, apressure-sensitive adhesive or a fiber processing and treating agent,which comprises the dispersion as defined in claim 1.